Photosensitive composition, image forming method, film forming method, resin, image, and film

ABSTRACT

Provided are a photosensitive composition containing a resin which includes a structural unit A represented by Formula (1) or (2) and a structural unit B represented by Formula (3), (4), or (5); and a radically polymerizable monomer, an image forming method, a film forming method, a resin, an image, and a film. R 11 , R 21 , R 31 , R 41 , and R 51  represent H or a hydrocarbon group, R 12  to R 14  and R 22  to R 24  represent a hydrocarbon group, H, or an OH group, R 42 , R 43 , R 52 , and R 53  represent H or a hydrocarbon group, L 1  to L 3  represent a single bond or a linking group, X 1  represents —O— or —NR 15 —, X 2  represent —O— or —NR 25 —, R 15  and R 25  represent H or a hydrocarbon group, and Cy 1  represents a hydrocarbon group which may contain O and has a cyclic structure.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of International Application No.PCT/JP2016/074706, filed Aug. 24, 2016, which claims priority toJapanese Patent Application No. 2015-167974 filed Aug. 27, 2015. Each ofthe above applications is hereby expressly incorporated by reference, inits entirety, into the present application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photosensitive composition, an imageforming method, a film forming method, a resin, an image, and a film.

2. Description of the Related Art

A photosensitive composition is known in various technical fields suchas ink compositions, coating compositions for film formation, coatingmaterials, printing plates, and electronic devices (a liquid crystaldisplay device, a solid-state imaging device, and a semiconductordevice).

For example, an active radiation curable ink composition including (A) apolymer which includes two or more acidic groups or two or more basicgroups; (B) a polymerizable monomer which includes a substituent groupcapable of forming a counter salt for the acidic groups or the basicgroups included in the polymer (A); (C) a photopolymerization initiator;and (D) a polymerizable monomer which has a structure different fromthat of the polymerizable monomer (B), as an ink composition which isexcellent in jetting stability even in a case where stored for a longperiod of time and has high sensitivity and in which an image obtainedby the composition being cured has excellent flexibility, excellentadhesiveness to a recording medium, and high surface hardness, is known(for example, see JP2011-225848A).

Further, as a lithographic printing plate original plate in whichdevelopment from an acidic region to a neutral region can be performedand which has overcome problems of developability during the developmentand dispersion stability of a protective layer component (developmentscum) removed by the development, a lithographic printing plate originalplate which includes (A) a sensitizing dye, (B) a polymerizationinitiator, (C) a polymerizable compound, (D) a photosensitive layercontaining a binder polymer, and a protective layer containing at leastone kind of acid-modified polyvinyl alcohol in a content of 50% by massor greater based on the total solid content of the protective layer inorder on a hydrophilic support and in which the protective layer and thephotosensitive layer of an unexposed portion can be removed by adeveloper whose pH is in a range of 2 to 8 is known (for example, seeJP2009-139852A).

Further, as a photopolymerizable resin composition which is highlysensitive to light in a wavelength range of 300 nm to 600 nm, includingvisible light, a photopolymerizable resin composition containing a vinylpolymer which has a specific structural unit including a dialkylaminogroup and an α-diketone which has a specific structure is known (forexample, see JP1993-142773A (JP-H05-142773A)).

Further, as an ink composition which has excellent curing sensitivity,scratch resistance, and blocking resistance, and in which stickiness ofthe surface is suppressed and an image with improved surface curabilitycan be formed, an ink composition containing a polymer which includes(a) a partial structure selected from the group consisting of afluorine-substituted hydrocarbon group, a siloxane skeleton, and along-chain alkyl group, a radically polymerizable group, and a tertiaryamine structure is known (for example, see JP2009-209352A).

Further, as a dye-containing negative curable composition which iscapable of forming an excellent pattern shape without developmentresidual films and residues even in a case where the pixel size becomesfiner, a dye-containing negative curable composition containing (A) anorganic solvent-soluble dye; (B) a photopolymerization initiator; (C) apolymerizable compound; (D) an amino group-containing alkali-solubleresin which includes a substituted or unsubstituted amino group in theside chain; and (E) an organic solvent is known (for example, seeJP2010-85553A).

SUMMARY OF THE INVENTION

However, in regard to the respective photosensitive compositionsdescribed in JP2011-225848A, JP2009-139852A, JP1993-142773A(JP-H05-142773A), JP2009-209352A, and JP2010-85553A, further improvementof storage stability, hardness of a formed film, and adhesiveness to asubstrate are required in some cases.

The present invention has been made in consideration of theabove-described problems and the task thereof is to achieve thefollowing objects.

In other words, an object of the present invention is to provide aphotosensitive composition which is capable of forming a film havingexcellent hardness and excellent adhesiveness to a substrate and hasexcellent storage stability, and an image forming method and a filmforming method using the above-described photosensitive composition.

Further, another object of the present invention is to provide a resinhaving a new structure, and an image and a film containing the resin.

Specific means for solving the above-described problems includes thefollowing aspects.

<1> A photosensitive composition containing: a resin which includes astructural unit A represented by Formula (1) or (2) and a structuralunit B represented by Formula (3), (4), or (5); and a radicallypolymerizable monomer.

In Formula (1), R¹¹ represents a hydrogen atom or a hydrocarbon group,R¹², R¹³, and R¹⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group, L¹ represents a single bond or adivalent linking group, X¹ represents a —O— group or a —NR¹⁵— group, andR¹⁵ represents a hydrogen atom or a hydrocarbon group.

In Formula (2), R²¹ represents a hydrogen atom or a hydrocarbon group,R²² represents a hydrocarbon group, which may be substituted with ahalogen atom and contain an oxygen atom, a hydrogen atom, or a hydroxylgroup, R²³ and R²⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group or R²³ and R²⁴ are integrated torepresent an oxygen atom, L² represents a single bond or a divalentlinking group, X² represents a —O— group or a —NR²⁵— group, and R²⁵represents a hydrogen atom or a hydrocarbon group.

In Formula (3), R³¹ represents a hydrogen atom or a hydrocarbon group,L³ represents a single bond or a divalent linking group, and Cy¹represents a hydrocarbon group which may contain an oxygen atom and hasa cyclic structure.

In Formula (4), R⁴¹ represents a hydrogen atom or a hydrocarbon group,R⁴² and R⁴³ each independently represent a hydrocarbon group which maycontain an oxygen atom, or a hydrogen atom, and R⁴² and R⁴³ may bebonded to each other and form a ring.

In Formula (5), R⁵¹ represents a hydrogen atom or a hydrocarbon group,R⁵² and R⁵³ each independently represent a hydrogen atom or ahydrocarbon group, and R⁵² and R⁵³ may be bonded to each other and forma ring.

<2> The photosensitive composition according to <1>,

in Formula (1), R¹¹ represents a hydrogen atom or an alkyl group having1 to 3 carbon atoms, R¹², R¹³, and R¹⁴ each independently represent ahydrocarbon group having 1 to 12 carbon atoms, which may be substitutedwith a halogen atom and contain an oxygen atom, a hydrogen atom, or ahydroxyl group, L¹ represents a single bond, an alkylene group having 1to 3 carbon atoms, or a group represented by any one of Formulae (L11)to (L14), and R¹⁵ represents a hydrogen atom or an alkyl group having 1to 3 carbon atoms,

in Formula (2), R²¹ represents a hydrogen atom or an alkyl group having1 to 3 carbon atoms, R²² represents a hydrocarbon group having 1 to 12carbon atoms, which may be substituted with a halogen atom and containan oxygen atom, a hydrogen atom, or a hydroxyl group, R²³ and R²⁴ eachindependently represent a hydrocarbon group having 1 to 12 carbon atoms,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group or R²³ and R²⁴ are integrated torepresent an oxygen atom, L² represents an alkylene group having 1 to 3carbon atoms or a group represented by any one of Formulae (L21) to(L24), and R²⁵ represents a hydrogen atom or an alkyl group having 1 to3 carbon atoms,

in Formula (3), R³¹ represents a hydrogen atom or an alkyl group having1 to 3 carbon atoms, L³ represents a single bond, an alkylene grouphaving 1 to 3 carbon atoms, or a group represented by any one ofFormulae (L31) to (L34), and Cy¹ represents a hydrocarbon group whichmay contain an oxygen atom, has a cyclic structure, and has 3 to 20carbon atoms,

in Formula (4), R⁴¹ represents a hydrogen atom or an alkyl group having1 to 3 carbon atoms, and R⁴² and R⁴³ each independently represent ahydrogen atom or an alkyl group having 1 to 6 carbon atoms or R⁴² andR⁴³ are bonded to each other and represent a group represented by anyone of Formulae (N41) to (N44), and

in Formula (5), R⁵¹ represents a hydrogen atom or an alkyl group having1 to 3 carbon atoms, and R⁵² and R⁵³ each independently represent ahydrogen atom or an alkyl group having 1 to 6 carbon atoms or R⁵² andR⁵³ are bonded to each other and represent a group represented byFormula (N51) or (N52).

In Formula (L11), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to X¹, and *2 represents a binding position withrespect to a carbon atom.

In Formula (L12), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to X¹, and *2represents a binding position with respect to a carbon atom.

In Formula (L13), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to X¹, and *2 represents a binding position with respect to acarbon atom.

In Formula (L14), *1 represents a binding position with respect to X¹,and *2 represents a binding position with respect to a carbon atom.

In Formula (L21), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to X², and *2 represents a binding position withrespect to a carbon atom.

In Formula (L22), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to X², and *2represents a binding position with respect to a carbon atom.

In Formula (L23), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to X², and *2 represents a binding position with respect to acarbon atom.

In Formula (L24), *1 represents a binding position with respect to X²,and *2 represents a binding position with respect to a carbon atom.

In Formula (L31), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to an oxygen atom, and *2 represents a bindingposition with respect to Cy¹.

In Formula (L32), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to an oxygen atom,and *2 represents a binding position with respect to Cy¹.

In Formula (L33), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to an oxygen atom, and *2 represents a binding position withrespect to Cy¹.

In Formula (L34), *1 represents a binding position with respect to anoxygen atom, and *2 represents a binding position with respect to Cy¹.

In Formulae (N41) to (N44), *1 and *2 represent a binding position withrespect to a nitrogen atom.

In Formulae (N51) and (N52), *1 represents a binding position withrespect to a nitrogen atom, and *2 represents a binding position withrespect to a carbon atom.

<3> The photosensitive composition according to <1> or <2>, in which thetotal content of the structural unit A and the structural unit B in theresin is 80% by mass or greater based on the total amount of the resin.

<4> The photosensitive composition according to any one of <1> to <3>,in which the proportion of the structural unit A in the total content ofthe structural unit A and the structural unit B in the resin is in arange of 10% by mass to 90% by mass.

<5> The photosensitive composition according to any one of <1> to <4>,in which the structural unit A is at least one structural unit Cselected from the group consisting of a structural unit represented byFormula (1-1), a structural unit represented by Formula (1-2), astructural unit represented by Formula (1-3), a structural unitrepresented by Formula (1-4), a structural unit represented by Formula(1-5), a structural unit represented by Formula (1-6), a structural unitrepresented by Formula (1-7), a structural unit represented by Formula(1-8), and a structural unit represented by Formula (2-1).

<6> The photosensitive composition according to any one of <1> to <5>,in which the structural unit B is at least one structural unit Dselected from the group consisting of a structural unit represented byFormula (3-3), a structural unit represented by Formula (3-4), astructural unit represented by Formula (3-5), a structural unitrepresented by Formula (4-1), a structural unit represented by Formula(4-2), a structural unit represented by Formula (4-3), a structural unitrepresented by Formula (4-4), a structural unit represented by Formula(5-1), a structural unit represented by Formula (5-2), and a structuralunit represented by Formula (5-3).

<7> The photosensitive composition according to any one of <1> to <4>,in which Cy¹ in Formula (3) includes a polycyclic structure as thecyclic structure, and R⁴¹ in Formula (4) represents a hydrogen atom.

<8> The photosensitive composition according to any one of <1> to <7>,in which the structural unit B includes at least one structural unitrepresented by Formula (3) and further includes at least one selectedfrom the group consisting of structural units represented by Formulae(4) and (5).

<9> The photosensitive composition according to any one of <1> to <8>,in which the weight-average molecular weight of the resin is in a rangeof 1000 to 50000.

<10> The photosensitive composition according to any one of <1> to <9>,in which the content of the resin is in a range of 0.5% by mass to 10.0%by mass based on the total amount of the photosensitive composition.

<11> The photosensitive composition according to any one of <1> to <10>,in which the radically polymerizable monomer includes a monofunctionalradically polymerizable monomer.

<12> The photosensitive composition according to any one of <1> to <11>,in which the content of the radically polymerizable monomer is 50% bymass or greater based on the total amount of the photosensitivecomposition.

<13> The photosensitive composition according to any one of <1> to <12>,further containing a photopolymerization initiator.

<14> An image forming method comprising: an application process ofapplying an ink composition which is the photosensitive compositionaccording to any one of <1> to <13> onto a recording medium according toan ink-jet method; and an irradiation process of irradiating the inkcomposition applied onto the recording medium with active energy rays.

<15> A film forming method comprising: an application process ofapplying the photosensitive composition according to any one of <1> to<13> onto a substrate; and an irradiation process of irradiating thephotosensitive composition applied onto the substrate with active energyrays.

<16> A resin comprising: at least one structural unit C selected fromthe group consisting of a structural unit represented by Formula (1-1),a structural unit represented by Formula (1-2), a structural unitrepresented by Formula (1-3), a structural unit represented by Formula(1-4), a structural unit represented by Formula (1-5), a structural unitrepresented by Formula (1-6), a structural unit represented by Formula(1-7), a structural unit represented by Formula (1-8), and a structuralunit represented by Formula (2-1); and at least one structural unit Dselected from the group consisting of a structural unit represented byFormula (3-3), a structural unit represented by Formula (3-4), astructural unit represented by Formula (3-5), a structural unitrepresented by Formula (4-1), a structural unit represented by Formula(4-2), a structural unit represented by Formula (4-3), a structural unitrepresented by Formula (4-4), a structural unit represented by Formula(5-1), a structural unit represented by Formula (5-2), and a structuralunit represented by Formula (5-3).

<17> The resin according to <16>, in which the structural unit Dincludes at least one selected from the group consisting of a structuralunit represented by Formula (3-3), a structural unit represented byFormula (3-4), and a structural unit represented by Formula (3-5) andfurther includes at least one selected from the group consisting of astructural unit represented by Formula (4-1), a structural unitrepresented by Formula (4-2), a structural unit represented by Formula(4-3), a structural unit represented by Formula (4-4), a structural unitrepresented by Formula (5-1), a structural unit represented by Formula(5-2), and a structural unit represented by Formula (5-3).

<18> An image containing: the resin according to <16> or <17>.

<19> A film containing: the resin according to <16> or <17>.

According to the present invention, it is possible to provide aphotosensitive composition which is capable of forming a film havingexcellent hardness and excellent adhesiveness to a substrate and hasexcellent storage stability, and an image forming method and a filmforming method using the above-described photosensitive composition.

Further, according to the present invention, it is also possible toprovide a resin having a new structure, and an image and a filmcontaining the resin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, specific embodiments of the present invention will bedescribed in detail, but the present invention is not particularlylimited to the embodiments described below and can be implemented byappropriately adding modifications within the range not obstructing thepurpose of the present invention.

The numerical ranges shown using “to” in the present specificationindicate ranges including the numerical values described before andafter “to” as the lower limits and the upper limits.

In the present specification, in a case where a plurality of substancescorresponding to respective components in a composition are present, theamount of the respective components in the composition indicates thetotal amount of the plurality of substances present in the compositionunless otherwise noted.

In the present specification, the meaning of the term “process” includesnot only an independent process but also a process whose intendedpurpose is achieved even in a case where the process is not clearlydistinguished from other processes.

In the present specification, the “light” has a concept including activeenergy rays such as γ-rays, β-rays, electron beams, ultraviolet rays,visible light, and infrared rays.

In the present specification, ultraviolet rays are also referred to as“ultraviolet (UV) light.”

In the present specification, light generated from light emitting diode(LED) light sources is also referred to as “LED light.”

In the present specification, “(meth)acrylic acid” has a conceptincluding both of acrylic acid and methacrylic acid, “(meth)acrylate”has a concept including both of acrylate and methacrylate, and a“(meth)acryloyl group” has a concept including both of an acryloyl groupand a methacryloyl group.

In the present specification, ratios of respective structural units in aresin are also referred to as “copolymerization ratios.”

[Photosensitive Composition]

A photosensitive composition of the present invention contains a resinwhich includes a structural unit A represented by Formula (1) or (2) anda structural unit B represented by Formula (3), (4), or (5)(hereinafter, also referred to as a “specific resin”) and a radicallypolymerizable monomer.

In the photosensitive composition of the present invention, thestructural unit A is at least one structural unit selected from thegroup consisting of a structural unit represented by Formula (1) and astructural unit represented by Formula (2).

Further, in the photosensitive composition of the present invention, thestructural unit B is at least one structural unit selected from thegroup consisting of a structural unit represented by Formula (3), astructural unit represented by Formula (4), and a structural unitrepresented by Formula (5).

Hereinafter, the structural unit represented by Formula (1), thestructural unit represented by Formula (2), the structural unitrepresented by Formula (3), the structural unit represented by Formula(4), and the structural unit represented by Formula (5) are respectivelyreferred to as a unit (1), a unit (2), a unit (3), a unit (4), and aunit (5) in some cases.

Similarly, a structural unit represented by Formula (X) is referred toas a unit (X) in some cases.

In Formula (1), R¹¹ represents a hydrogen atom or a hydrocarbon group,and R¹², R¹³, and R¹⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group. L¹ represents a single bond or adivalent linking group, and X¹ represents a —O— group or a —NR¹⁵— group.R¹⁵ represents a hydrogen atom or a hydrocarbon group.

In Formula (2), R²¹ represents a hydrogen atom or a hydrocarbon group,and R²² represents a hydrocarbon group, which may be substituted with ahalogen atom and contain an oxygen atom, a hydrogen atom, or a hydroxylgroup. R²³ and R²⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group or R²³ and R²⁴ are integrated torepresent an oxygen atom (in other words, a group represented by ═O). L²represents a single bond or a divalent linking group, and X² representsa —O— group or a —NR²⁵— group. R²⁵ represents a hydrogen atom or ahydrocarbon group.

In Formula (3), R³¹ represents a hydrogen atom or a hydrocarbon group,L³ represents a single bond or a divalent linking group, and Cy¹represents a hydrocarbon group which may contain an oxygen atom and hasa cyclic structure.

In Formula (4), R⁴¹ represents a hydrogen atom or a hydrocarbon group,and R⁴² and R⁴³ each independently represent a hydrocarbon group whichmay contain an oxygen atom, or a hydrogen atom. R⁴² and R⁴³ may bebonded to each other and form a ring.

In Formula (5), R⁵¹ represents a hydrogen atom or a hydrocarbon group,and R⁵² and R⁵³ each independently represent a hydrogen atom or ahydrocarbon group. R⁵² and R⁵³ may be bonded to each other and form aring.

According to the photosensitive composition of the present invention, itis possible to form a film which has excellent hardness and excellentadhesiveness to a substrate. Further, the photosensitive composition ofthe present invention has excellent storage stability.

The reason why a film which has excellent hardness and excellentadhesiveness to a substrate can be formed by the photosensitivecomposition of the present invention is assumed as follows.

A specific resin which is one component of the photosensitivecomposition includes at least one structural unit selected from thegroup consisting of a unit (1) and a unit (2), as the structural unit A.

Both of the units (1) and (2) have a hindered amine structure, includesa carbon atom (hereinafter, also referred to as “α-carbon”) in theα-position with respect to a nitrogen atom of the hindered aminestructure, and further includes at least one hydrogen atom (hereinafter,also referred to as “α-hydrogen”) bonded to the α-carbon.

In Formulae (1) and (2), hydrogen atoms surrounded by circles shown bybroken lines indicate α-hydrogen.

It is considered that the structural unit A (that is, at least oneselected from the group consisting of the unit (1) and the unit (2))containing α-hydrogen has a function of suppressing a phenomenon (oxygeninhibition) in which radical polymerization of a radically polymerizablemonomer is inhibited by oxygen. For this reason, it is considered thatradical polymerization of a radically polymerizable monomer efficientlyproceeds at the time of irradiation with light by the photosensitivecomposition containing a specific resin, which has the structural unitA, and a radically polymerizable monomer.

Moreover, it is considered that the structural unit B (at least oneselected from the group consisting of the unit (3), the unit (4), andthe unit (5)) included in a specific resin contributes to hardness of afilm to be formed and adhesiveness to a substrate of this film.

Accordingly, it is considered that the effect resulting from thestructural unit A and the effect resulting from the structural unit Bare combined with each other and improve the hardness of a film to beformed and the adhesiveness to a substrate by the photosensitivecomposition containing a specific resin which has both of the structuralunit A and the structural unit B and a radically polymerizable monomer.

In addition, the reason why the photosensitive composition of thepresent invention has excellent storage stability is assumed as follows.

That is, it is considered that neither of the structural unit A and thestructural unit B contain an aminoalkyl group (specifically, anaminoalkyl group which does not have a hindered amine structure andcontains a primary amino group; an aminoalkyl group which does not havea hindered amine structure and contains a secondary amino group; and anaminoalkyl group which does not have a hindered amine structure andcontains a tertiary amino group) which may become a factor of loweringthe storage stability of the photosensitive composition and does nothave a hindered amine structure.

Particularly, it is considered that the structural unit A having ahindered amine structure greatly improves the storage stability of thephotosensitive composition, compared to a structural unit containing anaminoalkyl group which does not have a hindered amine structure.

Therefore, it is considered that the storage stability of thephotosensitive composition is improved by the photosensitive compositioncontaining a specific resin which has both of the structural units A andB.

In addition, according to the photosensitive composition of the presentinvention, it is possible to form a film having excellent blockingresistance (that is, a film whose stickiness is suppressed). The reasonfor this is considered to be the same as the reason for which a filmwith excellent hardness and excellent adhesiveness to a substrate can beformed.

Further, in a case where the photosensitive composition of the presentinvention is used as an ink composition for an ink jet (hereinafter,also referred to as an “ink composition”), the jetting stability thereoffrom an ink jet head is also excellent. The reason for this isconsidered to be the same as the reason for which the photosensitivecomposition has excellent storage stability.

For example, specific resins described in specific examples (A-24) and(A-7) of the paragraphs 0100 to 0103 of Patent Document 1(JP2011-225848A) do not have the above-described structural unit A (seecomparative resins a and c in “examples” described below). Further, aresin described in a specific example (A-25) of the paragraph 0103 ofthe same Document does not have the above-described structural unit B(see a comparative resin b in “examples” described below).

Further, PA-5 described in the paragraph 0219 of Patent Document 2(JP-2009-139852A) does not have the above-described structural unit A(see a comparative resin d in “examples” described below).

As described above, specific resins containing both of the structuralunits A and B are not disclosed in any of JP2011-225848A,JP2009-139852A, JP1993-142773A (JP-H05-142773A), JP2009-209352A, andJP2010-85553A.

As described above, the structural unit A in the present inventionincludes at least one selected from the group consisting of the unit (1)and the unit (2), but it is particularly preferable that the structuralunit A includes at least one selected from the group consisting of theunit (1) from viewpoints of the hardness and blocking resistance of afilm.

Further, a specific resin may have other structural units other than thestructural units A and B within the range in which the effects of thepresent invention are not impaired.

Further, the specific resin may have only one kind of structural unit Aor may have two or more kinds thereof.

Further, the specific resin may have only one kind of structural unit Bor may have two or more kinds thereof.

In this case, from a viewpoint of more effectively exhibiting theeffects of the present invention, the total content of the structuralunits A and B is preferably 80% by mass or greater, more preferably 90%by mass or greater, still more preferably 95% by mass or greater, andideally 100% by mass based on the total amount of the specific resin.

Moreover, the proportion of the structural unit A in the total contentof the structural units A and B in the specific resin is notparticularly limited.

The proportion is preferably in a range of 10% by mass to 90% by mass,more preferably in a range of 20% by mass to 80% by mass, andparticularly preferably in a range of 30% by mass to 70% by mass.

In a case where the proportion thereof is 10% by mass or greater, theadhesiveness of a film to a substrate and the blocking resistance of thefilm are further improved.

In a case where the proportion thereof is 90% by mass or less, theadhesiveness of a film to a substrate is further improved.

Moreover, as a preferable range of the proportion of the structural unitA in the total amount of the specific resin, the same range as thepreferable range of the proportion of the structural unit A in the totalcontent of the structural units A and B is exemplified.

In addition, from the viewpoint of more effectively exhibiting theeffects of the present invention, it is preferable that the structuralunit A is at least one structural unit C selected from the groupconsisting of the following units (1-1) to (1-8) and (2-1).

From the viewpoint of the blocking resistance, it is preferable that thespecific resin includes at least one selected from the units (1-1),(1-2), (1-4), and (1-8) from among the units (1-1) to (1-8) and (2-1).

Further, from the viewpoints of the hardness and the blocking resistanceof a film, it is particularly preferable that the specific resinincludes the unit (1-1) from among the units (1-1) to (1-8) and (2-1).

Further, from the viewpoint of effectively exhibiting the effects of thepresent invention (particularly from the viewpoints of the blockingresistance of a film and the adhesiveness of the film to a substrate),it is preferable that the structural unit B is at least one structuralunit D selected from the group consisting of the following units (3-3)to (3-5), (4-1) to (4-4), and (5-1) to (5-3).

From the viewpoints of the hardness of a film, the blocking resistanceof the film, and the adhesiveness of the film to a substrate, it ispreferable that the specific resin includes at least one unit selectedfrom the units (4-1) to (4-3), (5-1), and (5-2) from among the units(3-3) to (3-5), (4-1) to (4-4), and (5-1) to (5-3).

Moreover, in the specific resin, it is preferable that Cy¹ in Formula(3) has a polycyclic structure as a cyclic structure and R⁴¹ in Formula(4) represents a hydrogen atom.

In such a mode, the blocking resistance of a film and the adhesivenessof the film to a substrate are further improved.

Moreover, the weight-average molecular weight (Mw) of the specific resinis not particularly limited, and the weight-average molecular weight(Mw) of the specific resin may be in a range of, for example, 1000 to100000.

From the viewpoint of the hardness of a film, the weight-averagemolecular weight (Mw) of the specific resin is preferably 1000 orgreater, more preferably 2000 or greater, and particularly preferably3000 or greater.

From the viewpoints of the storage stability and the jetting stabilityin a case where the photosensitive composition is used as an inkcomposition, the weight-average molecular weight (Mw) of the specificresin is preferably 50000 or less, more preferably 40000 or less, andparticularly preferably 30000 or less.

In the present specification, the weight-average molecular weight (Mw)indicates a value measured by gel permeation chromatography (GPC).

The measurement with gel permeation chromatography (GPC) is performedusing HLC (registered trademark)-8020GPC (manufactured by TOSOHCORPORATION) as a measuring device; three of TSK gel (registeredtrademark) Super Multipore HZ-H (4.6 mmID×15 cm, manufactured by TOSOHCORPORATION) as a column; and tetrahydrofuran (THF) as an eluent.Moreover, the measurement is performed using an RI detector under theconditions of a sample concentration of 0.45% by mass, a flow rate of0.35 ml/min, a sample injection amount of 10 μl, and a measurementtemperature of 40° C.

The calibration curve is prepared from eight samples of “standardsamples TSK standard, polystyrene” (manufactured by TOSOH CORPORATION):“F-40,” “F-20,” “F-4,” “F-1,” “A-5000,” “A-2500,” “A-1000,” and“n-propylbenzene.”

In addition, only one kind or two or more kinds of the specific resinsmay be contained in the photosensitive composition of the presentinvention.

The content of the specific resin can be adjusted to be in a range of0.5% by mass to 10.0% by mass based on the total amount of thephotosensitive composition.

From the viewpoint of the hardness of a film, the content of thespecific resin is preferably 0.5% by mass or greater, more preferably1.0% by mass or greater, still more preferably 1.5% by mass or greater,and particularly preferably 2.0% by mass or greater based on the totalamount of the photosensitive composition.

From the viewpoints of the storage stability and the jetting stabilityin the case where the photosensitive composition is used as an inkcomposition, the content of the specific resin is preferably 10.0% bymass or less, more preferably 9.0% by mass or less, still morepreferably 8.0% by mass or less, and particularly preferably 7.0% bymass or less based on the total amount of the photosensitivecomposition.

Moreover, only one kind or two or more kinds of the radicallypolymerizable monomers may be contained in the photosensitivecomposition of the present invention.

It is preferable that the radically polymerizable monomers include atleast one monofunctional radically polymerizable monomer (in the presentspecification, also referred to as a “monofunctional monomer”).

In a case where the radically polymerizable monomers include amonofunctional radically polymerizable monomer, the compatibilitybetween the specific resin and the radically polymerizable monomer isfurther improved, and the storage stability and the jetting stability inthe case where the photosensitive composition is used as an inkcomposition is further improved.

From the viewpoint of the compatibility with the specific resin, it ispreferable that the monofunctional radically polymerizable monomersinclude at least one compound selected from the group consisting ofN-vinyl caprolactam, 2-phenoxyethyl acrylate (PEA), cyclictrimethylolpropane formal acrylate (CTFA), isobornyl acrylate (IBOA),tetrahydrofurfuryl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, octylacrylate, decyl acrylate, tridecyl acrylate, isodecyl acrylate, laurylacrylate, 3,3,5-trimethyl cyclohexyl acrylate (TMCHA), dicyclopentenylacrylate (DCPA), and 4-t-butylcyclohexyl acrylate.

Further, in the photosensitive composition, from the viewpoint of thehardness of a film, it is preferable that the radically polymerizablemonomers include a polyfunctional radically polymerizable monomer (inthe present specification, also referred to as a “polyfunctionalmonomer”).

Moreover, from the viewpoint of more effectively exhibiting the effectsof the present invention, the content of the radically polymerizablemonomer in the photosensitive composition is preferably 50% by mass orgreater, more preferably 60% by mass or greater, and particularlypreferably 65% by mass or greater based on the total amount of thephotosensitive composition.

The upper limit of the content of the radically polymerizable monomer isnot particularly limited, and the upper limit thereof can be set to, forexample, 95% by mass or can be set to 90% by mass.

Moreover, from the viewpoint of more effectively exhibiting the effectsof the present invention, it is preferable that the photosensitivecomposition includes at least one photopolymerization initiator.

From the viewpoint of curing sensitivity, it is preferable that thephotopolymerization initiator includes at least one selected from thegroup consisting of a carbonyl compound and an acyl phosphine oxidecompound.

The photosensitive composition of the present invention can be suitablyused as a liquid to form a film (for example, an image) on a substrate(for example, a recording medium).

As such a liquid, an ink composition used to form an image on asubstrate serving as a recording medium and a coating solution (forexample, a coating agent, an adhesive, or a coating material) used toform a coating film on a substrate can be exemplified.

It is particularly preferable that the photosensitive composition of thepresent invention is used for ink jet recording (that is, thephotosensitive composition of the present invention is used as an inkcomposition).

The ink composition which is one application of the photosensitivecomposition of the present invention may be an ink composition thatcontains a colorant or a transparent ink composition (also referred toas a “clear ink”) that does not contain a colorant.

The same applies to the coating solution which is another application ofthe photosensitive composition of the present invention.

The substrate used to form a film using the photosensitive compositionof the present invention is not particularly limited and, for example, aknown substrate can be used as a support or a recording material.

Examples of the substrate include paper, paper on which plastic (forexample, polyethylene, polypropylene, or polystyrene) is laminated, ametal plate (for example, a plate of a metal such as aluminum, zinc, orcopper), a plastic film (for example, a film of polyvinyl chloride (PVC)resin, cellulose diacetate, cellulose triacetate, cellulose propionate,cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,polyethylene terephthalate (PET), polyethylene (PE), polystyrene (PS),polypropylene (PP), polycarbonate (PC), polyvinyl acetal, or an acrylicresin), paper on which the above-described metal is laminated orvapor-deposited, and a plastic film on which the above-described metalis laminated or vapor-deposited.

Since the photosensitive composition of the present invention can form afilm having excellent adhesiveness on a substrate, the photosensitivecomposition is particularly suitable for use to form a film on anon-absorbable substrate.

Preferred examples of the non-absorbable substrate include plasticsubstrates such as a polyvinyl chloride (PVC) substrate, a polystyrene(PS) substrate, a polycarbonate (PC) substrate, a polyethyleneterephthalate (PET) substrate, a polypropylene (PP) substrate, and anacrylic resin substrate.

Hereinafter, the photosensitive composition of the present inventionwill be described in detail.

<Specific Resin>

The photosensitive composition of the present invention contains aspecific resin having the structural units A and B.

The preferable ranges (preferable ranges such as the proportion of thestructural units A and B, the total content of the structural units Aand B based on the total amount of the specific resin, the content ofthe specific resin based on the total amount of the photosensitivecomposition, and the weight-average molecular weight) of the specificresin are as described above.

As described above, the structural unit A is at least one selected fromthe group consisting of the unit (1) and the unit (2).

As described above, the structural unit B is at least one selected fromthe group consisting of the unit (3), the unit (4), and the unit (5).

Hereinafter, each unit will be described.

(Unit (1))

The unit (1) is a structural unit represented by Formula (1).

In Formula (1), R¹¹ represents a hydrogen atom or a hydrocarbon group,and R¹², R¹³, and R¹⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group. L¹ represents a single bond or adivalent linking group, and X¹ represents a —O— group or a —NR¹⁵— group.R¹⁵ represents a hydrogen atom or a hydrocarbon group.

As R¹¹, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms ispreferable, a hydrogen atom, a methyl group, or an ethyl group is morepreferable, and a hydrogen atom or a methyl group is particularlypreferable.

In R¹², the number of carbon atoms of the hydrocarbon group which may besubstituted with a halogen atom and contain an oxygen atom is preferablyin a range of 1 to 12, more preferably in a range of 1 to 3, still morepreferably 1 or 2, and particularly preferably 1.

Moreover, in the present specification, as the halogen atom in “thehydrocarbon group which may be substituted with a halogen atom andcontain an oxygen atom,” a fluorine atom, a chlorine atom, or a bromineatom is preferable and a fluorine atom or a chlorine atom is morepreferable.

Further, in the present specification, the expression “which may besubstituted with a halogen atom” in “the hydrocarbon group which may besubstituted with a halogen atom and contain an oxygen atom,” means thatthe hydrocarbon group may be substituted with at least one halogen atom.

In regard to “the hydrocarbon group which may contain an oxygen atom” inR¹², examples of the hydrocarbon group containing an oxygen atom includea hydrocarbon group substituted with an alkoxy group, a hydrocarbongroup substituted with an acyl group, a hydrocarbon group substitutedwith an acyloxy group, a hydrocarbon group substituted with analkoxycarbonyl group, a hydrocarbon group substituted with a hydroxylgroup, and a hydrocarbon group substituted with a carboxyl group.

As R¹², a hydrocarbon group, which may be substituted with a halogenatom, contain an oxygen atom, and has 1 to 12 carbon atoms, a hydrogenatom, or a hydroxyl group is preferable; a hydrogen atom, a hydroxylgroup, an alkyl group having 1 to 12 carbon atoms, a halogenated alkylgroup having 1 to 12 carbon atoms (preferably an alkyl chloride grouphaving 1 to 12 carbon atoms), an alkenyl group having 2 to 12 carbonatoms, an acyloxyalkyl group having 3 to 12 carbon atoms, an aryl grouphaving 6 to 12 carbon atoms (such as a phenyl group, a naphthyl group,or a biphenyl group), an aralkyl group having 7 to 12 carbon atoms (suchas a benzyl group), or an aryloxyalkyl group having 7 to 12 carbon atoms(such as a phenoxyethyl group) is preferable; a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, or an aryl group having 6 to 12carbon atoms is more preferable; a hydrogen atom or an alkyl grouphaving 1 to 3 carbon atoms is still more preferable; a hydrogen atom, amethyl group, or an ethyl group is even still more preferable; and ahydrogen atom or a methyl group is particularly preferable.

In R¹³ and R¹⁴, the number of carbon atoms of the hydrocarbon groupwhich may be substituted with a halogen atom and contain an oxygen atomis preferably in a range of 1 to 12.

Examples of “the hydrocarbon group which may contain an oxygen atom” inR¹³ and R¹⁴ are the same as those of the hydrocarbon group which maycontain an oxygen atom in R¹².

In R¹³ and R¹⁴, as the hydrocarbon group which may be substituted with ahalogen atom and contain an oxygen atom, an alkyl group having 1 to 12carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms(preferably an alkyl chloride group having 1 to 12 carbon atoms), analkenyl group having 2 to 12 carbon atoms, an acyloxyalkyl group having3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms (such asa phenyl group, a naphthyl group, or a biphenyl group), an aralkyl grouphaving 7 to 12 carbon atoms (such as a benzyl group), or an aryloxyalkylgroup having 7 to 12 carbon atoms (such as a phenoxyethyl group) ispreferable; an alkyl group having 1 to 12 carbon atoms or an aryl grouphaving 6 to 12 carbon atoms is more preferable; and an alkyl grouphaving 1 to 8 carbon atoms or a phenyl group is particularly preferable.

As R¹³ and R¹⁴, a hydrocarbon group which may be substituted with ahalogen atom, contain an oxygen atom, and has 1 to 12 carbon atoms, ahydrogen atom, or a hydroxyl group is preferable.

In L¹, as a divalent linking group, an alkylene group having 1 to 3carbon atoms or a group represented by any one of Formulae (L11) to(L14) is preferable.

In Formula (L11), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to X¹, and *2 represents a binding position withrespect to a carbon atom.

In Formula (L12), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to X¹, and *2represents a binding position with respect to a carbon atom.

In Formula (L13), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to X¹, and *2 represents a binding position with respect to acarbon atom.

In Formula (L14), *1 represents a binding position with respect to X¹,and *2 represents a binding position with respect to a carbon atom.

n in Formula (L11) is preferably an integer of 1 to 3, more preferablyan integer of 1 or 2, and particularly preferably an integer of 1.

X¹ represents a —O— group or a —NR¹⁵— group, and R¹⁵ represents ahydrogen atom or a hydrocarbon group.

As R¹⁵, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms ispreferable; a hydrogen atom, a methyl group, or an ethyl group is morepreferable; and a hydrogen atom or a methyl group is particularlypreferable.

A particularly preferable mode of Formula (1) is that R¹¹ represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, R¹², R¹³,and R¹⁴ each independently represent a hydrocarbon group, which may besubstituted with a halogen atom, contain an oxygen atom, and has 1 to 12carbon atoms, a hydrogen atom, or a hydroxyl group, L¹ represents asingle bond, an alkylene group having 1 to 3 carbon atoms, or a grouprepresented by any one of Formulae (L11) to (L14), and R¹⁵ represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Hereinafter, specific examples of the unit (1) (units (1-1) to (1-16))will be shown, but the unit (1) is not limited to the following specificexamples. Among the following specific examples, preferable units are asdescribed above.

(Unit (2))

The unit (2) is a structural unit represented by Formula (2).

In Formula (2), R²¹ represents a hydrogen atom or a hydrocarbon group,and R²² represents a hydrocarbon group, which may be substituted with ahalogen atom and contain an oxygen atom, a hydrogen atom, or a hydroxylgroup. R²³ and R²⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group or R²³ and R²⁴ are integrated torepresent an oxygen atom (in other words, a group represented by ═O, forexample, see the unit (2-3) described below). L² represents a singlebond or a divalent linking group, and X² represents a —O— group or a—NR²⁵— group. R²⁵ represents a hydrogen atom or a hydrocarbon group.

The preferable range of R²¹ in Formula (2) is the same as that of R¹¹ inFormula (1).

The preferable range of R²² in Formula (2) is the same as that of R¹² inFormula (1).

The preferable ranges of R²³ and R²⁴ in Formula (2) are respectively thesame as those of R¹³ and R¹⁴ in Formula (1), but it is also preferablethat R²³ and R²⁴ are integrated to represent an oxygen atom.

In L², as the divalent linking group, an alkylene group having 1 to 3carbon atoms or a group represented by any one of Formulae (L21) to (24)is preferable.

In Formula (L21), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to X², and *2 represents a binding position withrespect to a carbon atom.

In Formula (L22), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to X², and *2represents a binding position with respect to a carbon atom.

In Formula (L23), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to X², and *2 represents a binding position with respect to acarbon atom.

In Formula (L24), *1 represents a binding position with respect to X²,and *2 represents a binding position with respect to a carbon atom.

n in Formula (L21) is preferably an integer of 1 to 3, more preferably 1or 2, and particularly preferably 1.

X² represents a —O— group or a —NR²⁵— group, and R²⁵ represents ahydrogen atom or a hydrocarbon group.

As R²⁵, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms ispreferable; a hydrogen atom, a methyl group, or an ethyl group is morepreferable; and a hydrogen atom or a methyl group is particularlypreferable.

A particularly preferable mode of Formula (2) is that R²¹ represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, R²²represents a hydrocarbon group, which may be substituted with a halogenatom, contain an oxygen atom, and has 1 to 12 carbon atoms, a hydrogenatom, or a hydroxyl group, R²³ and R²⁴ each independently represent ahydrocarbon group, which may be substituted with a halogen atom, containan oxygen atom, and has 1 to 12 carbon atoms, a hydrogen atom, or ahydroxyl group or R²³ and R²⁴ are integrated to represent an oxygenatom, L² represents an alkylene group having 1 to 3 carbon atoms or agroup represented by any one of Formulae (L21) to (L24), and R²⁵represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Hereinafter, specific examples of the unit (2) (units (2-1) to (2-5))will be shown, but the unit (2) is not limited to the following specificexamples. Among the following specific examples, preferable units are asdescribed above.

(Unit (3))

The unit (3) is a structural unit represented by Formula (3).

In Formula (3), R³¹ represents a hydrogen atom or a hydrocarbon group,L³ represents a single bond or a divalent linking group, and Cy¹represents a hydrocarbon group which may contain an oxygen atom and hasa cyclic structure.

The preferable range of R³¹ in Formula (3) is the same as that of R¹¹ inFormula (1).

In L³, as the divalent linking group, an alkylene group having 1 to 3carbon atoms or a group represented by any one of Formulae (L31) to(L34) is preferable.

In Formula (L31), L represents an alkylene group having 1 to 3 carbonatoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to an oxygen atom, and *2 represents a bindingposition with respect to Cy¹.

In Formula (L32), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to an oxygen atom,and *2 represents a binding position with respect to Cy¹.

In Formula (L33), L¹ and L² each independently represent an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to an oxygen atom, and *2 represents a binding position withrespect to Cy¹.

In Formula (L34), *1 represents a binding position with respect to anoxygen atom, and *2 represents a binding position with respect to Cy¹.

n in Formula (L31) is preferably an integer of 1 to 3, more preferably 1or 2, and particularly preferably 1.

In Cy¹, the number of carbon atoms of the hydrocarbon group which maycontain an oxygen atom and has a cyclic structure is preferably in arange of 3 to 20, more preferably in a range of 6 to 20, still morepreferably in a range of 6 to 12, and particularly preferably in a rangeof 6 to 10.

Examples of the hydrocarbon group which may contain an oxygen atom andhas a cyclic structure include a substituted or unsubstituted arylgroup, a substituted or unsubstituted alicyclic group, a substituted orunsubstituted cyclic acetal group, a substituted or unsubstituted cyclicether group, a substituted or unsubstituted lactone group, and asubstituted or unsubstituted heteroaryl group which contains an oxygenatom as a heteroatom. As the substituent groups in the substituted arylgroup, the substituted alicyclic group, the substituted cyclic acetalgroup, the substituted cyclic ether group, the substituted lactonegroup, and the substituted heteroaryl group, an alkoxy group, an acylgroup, an acyloxy group, an alkoxycarbonyl group, a hydroxyl group, anda carboxyl group can be respectively exemplified.

Examples of the hydrocarbon group which may contain an oxygen atom andhas a cyclic structure include a phenyl group, a naphthyl group, abiphenyl group, a cyclohexyl group, an alkylcyclohexyl group, anorbornyl group, a dicyclopentanyl group, a dicyclopentenyl group, anadamantyl group, a furfuryl group, a hydrofurfuryl group, a cyclicacetal group, a cyclic ether group, and a lactone group.

A particularly preferable mode of Formula (3) is that R³¹ represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, L³represents a single bond, an alkylene group having 1 to 3 carbon atoms,or a group represented by any one of Formulae (L31) to (L34), and Cy¹represents a hydrocarbon group which may contain an oxygen atom, has acyclic structure, and has 3 to 20 carbon atoms.

Moreover, from the viewpoint of the blocking resistance of a film andthe adhesiveness of the film to a substrate, it is preferable that Cy¹has a polycyclic structure and more preferable that Cy¹ has a polycyclicalicyclic structure, as a cyclic structure.

Hereinafter, specific examples of the unit (3) (units (3-1) to (3-21))will be shown, but the unit (3) is not limited to the following specificexamples. Among the following specific examples, preferable units are asdescribed above.

(Unit (4))

The unit (4) is a structural unit represented by Formula (4).

In Formula (4), R⁴¹ represents a hydrogen atom or a hydrocarbon group,and R⁴² and R⁴³ each independently represent a hydrocarbon group whichmay contain an oxygen atom, or a hydrogen atom. R⁴² and R⁴³ may bebonded to each other (that is, R⁴² and R⁴³ are integrated) and form aring.

As R⁴¹, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms ispreferable; a hydrogen atom, a methyl group, or an ethyl group is morepreferable; a hydrogen atom or a methyl group is still more preferable;and a hydrogen atom is particularly preferable.

In R⁴² and R⁴³, the number of carbon atoms of the hydrocarbon groupwhich may contain an oxygen atom is preferably in a range of 1 to 6 andmore preferably in a range of 1 to 3.

In regard to the expression “the hydrocarbon group which may contain anoxygen atom” in R⁴² and R⁴³, examples of the hydrocarbon groupcontaining an oxygen atom are the same as those of the hydrocarbon groupcontaining an oxygen atom in R¹² in Formula (1).

From the viewpoint of the hardness of a film, it is preferable that R⁴²and R⁴³ in Formula (4) each independently represent a hydrocarbon groupwhich may contain an oxygen atom or R⁴² and R⁴³ are bonded to each other(that is, R⁴² and R⁴³ are integrated) and form a ring.

Further, in a case where R⁴² and R⁴³ are bonded to each other and form aring, it is preferable that R⁴² and R⁴³ represent a group represented byany one of Formulae (N41) to (N44).

In Formulae (N41) to (N44), *1 and *2 represent a binding position withrespect to a nitrogen atom.

A particularly preferable mode of Formula (4) is that R⁴¹ represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R⁴² andR⁴³ each independently represent a hydrogen atom or an alkyl grouphaving 1 to 3 carbon atoms or R⁴² and R⁴³ are bonded to each other andrepresent a group represented by any one of Formulae (N41) to (N44).

Among such modes, from the viewpoint of the hardness of a film, a morepreferable mode is that R⁴² and R⁴³ each independently represent analkyl group having 1 to 3 carbon atoms or R⁴² and R⁴³ are bonded to eachother (that is, R⁴² and R⁴³ are integrated) and represent a grouprepresented by any one of Formulae (N41) to (N44).

Hereinafter, specific examples of the unit (4) (units (4-1) to (4-12))will be shown, but the unit (4) is not limited to the following specificexamples. Among the following specific examples, preferable units are asdescribed above.

(Unit (5))

The unit (5) is a structural unit represented by Formula (5).

In Formula (5), R⁵¹ represents a hydrogen atom or a hydrocarbon group,and R⁵² and R⁵³ each independently represent a hydrogen atom or ahydrocarbon group. R⁵² and R⁵³ may be bonded to each other and form aring.

As R⁵¹, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms ispreferable; a hydrogen atom, a methyl group, or an ethyl group is morepreferable; a hydrogen atom or a methyl group is still more preferable;and a hydrogen atom is particularly preferable.

In R⁵² and R⁵³, the number of carbon atoms of the hydrocarbon group ispreferably in a range of 1 to 6 and more preferably in a range of 1 to3.

From the viewpoint of the hardness of a film, it is preferable that R⁵²and R⁵³ in Formula (5) each independently represent a hydrocarbon groupor R⁵² and R⁵³ are bonded to each other (that is, R⁵² and R⁵³ areintegrated) and form a ring.

Further, in a case where R⁵² and R⁵³ are bonded to each other and form aring, it is particularly preferable that the group formed by R⁵² and R⁵³being integrated is a group represented by Formula (N51) or (N52).

In Formula (N51) or (N52), *1 represents a binding position with respectto a nitrogen atom, and *2 represents a binding position with respect toa carbon atom.

A preferable mode of Formula (5) is that R⁵¹ represents a hydrogen atomor an alkyl group (preferably a hydrogen atom) having 1 to 3 carbonatoms, and R⁵² and R⁵³ each independently represent a hydrogen atom oran alkyl group having 1 to 6 carbon atoms or R⁵² and R⁵³ are bonded toeach other (that is, R⁵² and R⁵³ are integrated) and represent a grouprepresented by Formula (N51) or (N52).

Among such modes, from the viewpoint of the hardness of a film, a morepreferable mode is that R⁵² and R⁵³ each independently represent analkyl group having 1 to 6 carbon atoms or R⁵² and R⁵³ are bonded to eachother and represent a group represented by Formula (N51) or (N52).

Hereinafter, specific examples of the unit (5) (units (5-1) to (5-5))will be shown, but the unit (5) is not limited to the following specificexamples. Among the following specific examples, preferable units are asdescribed above.

A particularly preferable combination of the structural units A and B inthe specific resin is that the structural unit A includes the unit (1-1)and the structural unit B includes at least one selected from the units(4-1) to (4-3), (5-1), and (5-2).

A more preferable combination thereof is that the structural unit Aincludes the unit (1-1) and the structural unit B includes at least oneselected from the units (4-3) and (5-2).

A particularly preferable combination thereof is that the structuralunit A includes the unit (1-1) and the structural unit B includes bothof the units (4-3) and (5-2).

Further, from the viewpoints of forming a film with excellent hardnessand adhesiveness to the substrate and improving jetting properties, aparticularly preferable combination is that the structural unit Aincludes the unit (1-1) and the structural unit B includes at least oneof the unit (3-3), the unit (3-4), or the unit (3-5) and at least one ofthe unit (4-3), the unit (5-1), or the unit (5-2). Further, a still morepreferable combination is that the structural unit A includes the unit(1-1) and the structural unit B includes at least one of the unit (3-3),the unit (3-4), or the unit (3-5) and the unit (5-2).

(Other Structural Units)

The specific resin may include other structural units other than thestructural units A and B.

As other structural units, for example, structural units derived from avinyl monomer can be suitably selected and used.

In this case, as described above, the total content of the structuralunits A and B is preferably 80% by mass or greater, more preferably 90%by mass or greater, still more preferably 95% by mass or greater, andideally 100% by mass based on the total amount of the specific resin.

Moreover, the specific resin may include a structural unit having anaminoalkyl group as other structural units other than the structuralunits A and B within the range in which the storage stability of thephotosensitive composition is not impaired.

In this case, from the viewpoint of the storage stability of thephotosensitive composition, the content of the structural unit having anaminoalkyl group, as other structural units, is preferably 10% by massor less, more preferably 3% by mass or less, and still more preferably1% by mass or less based on the total amount of the specific resin. Fromthe viewpoint of the storage stability of the photosensitivecomposition, a particularly preferable mode is that the specific resindoes not include a structural unit having an aminoalkyl group, as otherstructural units.

<Radically Polymerizable Monomer>

The photosensitive composition of the present invention contains aradically polymerizable monomer (hereinafter, also simply referred to asa “polymerizable monomer”). Only one kind or two or more kinds of thepolymerizable monomers may be contained in the photosensitivecomposition.

The preferable ranges of the content of the polymerizable monomer basedon the total amount of the photosensitive composition are as describedabove.

It is preferable that a compound including at least one ethylenic doublebond in a molecule is used as the polymerizable monomer.

As the polymerizable monomer, known polymerizable monomers described inthe paragraphs 0108 to 0137 of JP2011-225848A, the paragraphs 0150 to0188 of JP2009-139852A, and the paragraphs 0122 to 0127 ofJP2009-209352A can be used.

As the polymerizable monomer, a monofunctional polymerizable monomer, apolyfunctional polymerizable monomer, or a combination of amonofunctional polymerizable monomer and a polyfunctional polymerizablemonomer may be used.

The monofunctional polymerizable monomer is advantageous in that theviscosity of the photosensitive composition is decreased and the jettingstability in the case where the photosensitive composition is used as anink composition is improved.

The polyfunctional polymerizable monomer is advantageous in terms of thehardness of a film.

Examples of the monofunctional polymerizable monomer include an N-vinylcompound such as N-vinylcaprolactam or N-vinylpyrrolidone; amonofunctional acrylate compound such as 2-phenoxyethyl acrylate (PEA),benzyl acrylate, cyclic trimethylolpropane formal acrylate (CTFA),isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate,2-(2-ethoxyethoxy)ethyl acrylate, octyl acrylate, decyl acrylate,tridecyl acrylate, isodecyl acrylate, lauryl acrylate, 3,3,5-trimethylcyclohexyl acrylate (TMCHA), dicyclopentenyl acrylate (DCPA),4-t-butylcyclohexyl acrylate, cyclohexyl acrylate, caprolactone-modifiedacrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, polyethyleneglycol acrylate, polypropylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, or nonylphenoxy polypropylene glycolacrylate; a monofunctional methacrylate compound such as 2-phenoxyethylmethacrylate, benzyl methacrylate, isobornyl methacrylate (IBOA),tetrahydrofurfuryl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate,octyl methacrylate, decyl methacrylate, tridecyl methacrylate, isodecylmethacrylate, lauryl methacrylate, 3,3,5-trimethyl cyclohexylmethacrylate (TMCHA), dicyclopentenyl methacrylate (DCPA),4-t-butylcyclohexyl methacrylate, cyclohexyl methacrylate,caprolactone-modified methacrylate, hydroxyethyl methacrylate,hydroxybutyl methacrylate, polyethylene glycol methacrylate,polypropylene glycol methacrylate, nonylphenoxy polyethylene glycolmethacrylate, or nonylphenoxy polypropylene glycol methacrylate; amonofunctional vinyl ether compound such as N-propyl vinyl ether,isopropyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether,2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxy ethyl vinylether, 4-hydroxybutyl vinyl ether, or cyclohexane dimethanol monovinylether; a monofunctional acrylamide compound such as acrylamide,N,N-diemthylacrylamide, N,N-diethylacrylamide, acryloylmorpholine,N-isopropylacrylamide, N-hydroxyethyl acrylamide, N-butyl acrylamide,N-tert-butyl acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide,N-dodecyl acrylamide, or N-(buthoxymethyl)acrylamide; and amonofuctional methacrylamide compound such as methacrylamide,N-phenylmethacrylamide, N-(methoxymethyl)methacrylamide,N,N-dimethylmethacrylate, or N-tert-butylmethacrylamide.

From the viewpoint of the compatibility with the specific resin,preferable examples of the monofunctional polymerizable monomer are asdescribed above.

Examples of the polyfunctional polymerizable monomer include apolyfunctional acrylate compound such as hexanediol diacrylate (HDDA),dipropylene glycol diacrylate (DPGDA), polyethylene glycol diacrylate,polypropylene glycol diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate (DPHA), trimethylolpropane triacrylate,ditrimethylolpropane tetraacrylate, nonanediol diacrylate, decanedioldiacrylate, neopentyl glycol diacrylate, polyethylene glycol-modifiedbisphenol A diacrylate, dioxane glycol diacrylate, cyclohexanedimethanol diacrylate, or tricyclodecane dimethanol diacrylate;2-(2-vinyloxyethoxy)ethylacrylate (VEEA); a polyfunctional vinylcompound such as 1,4-butanediol divinyl ether, cyclohexanedimethanoldivinyl ether, diethylene glycol divinyl ether, or triethylene glycoldivinyl ether (DVE3); and a polyfunctional methacrylate compound such ashexanediol dimethacrylate, dipropylene glycol dimethacrylate (DPGDA),polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate,pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,neopentyl glycol dimethacrylate, or polyethylene glycol-modifiedbisphenol A dimethacrylate.

In addition to the above-described polymerizable compounds, commerciallyavailable products described in “Cross-linking Agent Handbook” (1981,edited by Shinzo Yamashita, published by Taiseisha, Ltd.), “UV⋅EB CuringHandbook (part of raw materials)” (1985, edited by Kiyoshi Kato,published by Kobunshi Kankokai), “Application and Market of UV⋅EB CuringTechnology” (pp. 79, 1989, edited by Rad Tech Japan, CMC Publishing Co.,Ltd.), “Polyester Resin Handbook” (1988, written by Eiichiro Takiyama,published by Nikkan Kogyo Shimbun, Ltd.); and a radically polymerizablemonomer which is known in the field can be used.

As polymerizable monomers, commercially available products on the marketmay be used. Examples of the commercially available products of thepolymerizable monomers include ethoxylated or propoxylated acrylate suchas AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G,DAUA-167 (all manufactured by KYOEISHA CHEMICAL Co., LTD.), SR444,SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR494 (allmanufactured by Sartomer Company), and an isocyanuric monomer such asA-9300, A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co.,Ltd.).

Moreover, other commercially available products of the polymerizablemonomers include neopentyl glycol propylene oxide adduct diacrylate(NPGPODA, manufactured by Sartomer Company), dipentaerythritolpentaacrylate (SR399E, manufactured by Sartomer Company),pentaerythritol triacrylate (ATMM-3L, manufactured by Shin-NakamuraChemical Co., Ltd.), and dipentaerythritol hexaacrylate (A-DPH,manufactured by Shin-Nakamura Chemical Co., Ltd.).

The weight-average molecular weight of the polymerizable monomer ispreferably 100 to less than 1,000, more preferably in a range of 100 to800, and still more preferably in a range of 150 to 700.

The weight-average molecular weight of the polymerizable monomer is avalue measured by gel permeation chromatography (GPC).

Preferable ranges of the content of the polymerizable monomer are asdescribed above.

<Radically Polymerizable Resin>

The photosensitive composition of the present invention can contain aradically polymerizable resin (hereinafter, also simply referred to as a“polymerizable resin”). In this case, only one kind or two or more kindsof the polymerizable resins may be contained in the photosensitivecomposition.

In a case where the photosensitive composition of the present inventioncontains a radically polymerizable resin, the effects of theabove-described structural unit A (effects of suppressing a phenomenonin which radical polymerization is inhibited by oxygen) are exhibitedwith respect to radical polymerization of the radically polymerizablemonomer and radical polymerization of the radically polymerizable resin.

Here, the polymerizable resin indicates a resin including apolymerizable group.

The concept of the polymerizable resin includes an oligomer including apolymerizable group and a polymer including a polymerizable group.

Examples of the resin which is the base of the polymerizable resininclude an acrylic resin, a urethane resin, a polyester resin, apolyether resin, a polycarbonate resin, an epoxy resin, and apolybutadiene resin. Among these, from a viewpoint of reducing curingcontraction, a resin which includes both of a hard segment and a softsegment and in which the stress at the time of curing can be relaxed ispreferable and at least one resin selected particularly from a urethaneresin, a polyester resin, and an epoxy resin is more preferable.

As the polymerizable group contained in the polymerizable resin, a groupincluding an ethylenic double bond is preferable and a group includingat least one of a vinyl group and a 1-methylvinyl group is morepreferable.

From the viewpoint of polymerization reactivity and the hardness of afilm to be formed, a (meth)acryloyl group is particularly preferable asthe polymerizable group.

These polymerizable groups can be introduced into a resin (a polymer oran oligomer) through a polymer reaction or copolymerization.

For example, a polymerizable group can be introduced into a polymer (oran oligomer) using a reaction of a polymer (or an oligomer) including acarboxy group in the side chain thereof with glycidyl methacrylate or areaction of a polymer (or an oligomer) including an epoxy group withethylenically unsaturated group-containing carboxylic acid such asmethacrylic acid. These groups may be used in combination.

As the polymerizable resin, commercially available products in themarket may be used.

Examples of the commercially available products of the acrylic resinincluding a polymerizable group include (ACA)Z200M, (ACA)Z230AA,(ACA)Z251, (ACA)Z254F (all manufactured by DAICEL-ALLNEX. LTD.), andHITALOID 7975D (manufactured by Hitachi Chemical Co., Ltd.).

Examples of the commercially available products of the urethane resinincluding a polymerizable group include EBECRYL (registered trademark)8402, EBECRYL (registered trademark) 8405, EBECRYL (registeredtrademark) 9270, EBECRYL (registered trademark) 8311, EBECRYL(registered trademark) 8701, KRM 8667, KRM 8528 (all manufactured byDAICEL-ALLNEX. LTD.), CN964, CN9012, CN968, CN996, CN975, CN9782 (allmanufactured by Sartomer Company), UV-6300B, UV-7600B, UV-7605B,UV-7620EA, UV-7630B (all manufactured by Nippon Synthetic ChemicalIndustry Co., Ltd.), U-6HA, U-15HA, U-108A, U-200PA, UA-4200 (allmanufactured by Shin-Nakamura Chemical Co., Ltd.), TESLAC 2300, HITALOID4863, TESLAC 2328, TESLAC 2350, HITALOID 7902-1 (all manufactured byHitachi Chemical Co., Ltd.), 8UA-017, 8UA-239, 8UA-239H, 8UA-140,8UA-585H, 8UA-347H, and 8UX-015A (all manufactured by TAISEI FINECHEMICAL CO., LTD.).

Examples of the commercially available products of the polyester resinincluding a polymerizable group include CN294, CN2254, CN2260, CN2271E,CN2300, CN2301, CN2302, CN2303, CN2304 (all manufactured by SartomerCompany), EBECRYL (registered trademark) 436, EBECRYL (registeredtrademark) 438, EBECRYL (registered trademark) 446, EBECRYL (registeredtrademark) 524, EBECRYL (registered trademark) 525, EBECRYL (registeredtrademark) 811, and EBECRYL (registered trademark) 812 (all manufacturedby DAICEL-ALLNEX. LTD.).

Examples of the commercially available products of the polyether resinincluding a polymerizable group include BLEMMER (registered trademark)ADE-400A and BLEMMER (registered trademark) ADP-400 (both manufacturedby NOF CORPORATION).

Examples of the commercially available products of the polycarbonateresin including a polymerizable group include polycarbonate dioldiacrylate (manufactured by Ube Industries, Ltd.).

Examples of the commercially available products of the epoxy resinincluding a polymerizable group include EBECRYL (registered trademark)3708 (manufactured by DAICEL-ALLNEX. LTD.), CN120, CN120B60, CN120B80,CN120E50 (all manufactured by Sartomer Company), and HITALOID 7851(manufactured by Hitachi Chemical Co., Ltd.).

Examples of the commercially available products of the polybutadieneresin including a polymerizable group include CN301, CN303, and CN307(all manufactured by Satomer Company).

From the viewpoint of balancing the adhesiveness and the dispersionstability, the weight-average molecular weight of the polymerizableresin is preferably in a range of 1,000 to 100,000, more preferably in arange of 1,000 to 40,000, and still more preferably in a range of 1,000to 10,000.

The weight-average molecular weight of the polymerizable resin is avalue measured by gel permeation chromatography (GPC).

In a case where the photosensitive composition of the present inventioncontains a polymerizable resin, from the viewpoint of effectivelyexhibiting the effects of the present invention, the content of thepolymerizable resin is preferably in a range of 0.1% by mass to 10% bymass, more preferably in a range of 0.3% by mass to 5.0% by mass, andparticularly preferably in a range of 1.0% by mass to 3.0% by mass basedon the total amount of the photosensitive composition.

<Photopolymerization Initiator>

It is preferable that the photosensitive composition of the presentinvention contains a photopolymerization initiator.

In a case where the photosensitive composition of the present inventioncontains a photopolymerization initiator, one kind or two or more kindsof the photopolymerization initiators may be contained.

A known photopolymerization initiator which absorbs light (that is,active energy rays) and generates a radical that is a polymerizationinitiator species can be used as a photopolymerization initiator.

Preferred examples of the photopolymerization initiator include (a)carbonyl compounds such as aromatic ketones, (b) an acyl phosphine oxidecompound, (c) an aromatic onium salt compound, (d) an organic peroxide,(e) a thio compound, (f) a hexaarylbiimidazole compound, (g) a ketoximeester compound, (h) a borate compound, (i) an azinium compound, (j) ametallocene compound, (k) an active ester compound, (l) a compoundhaving a carbon-halogen bond, and (m) an alkylamine compound.

The compounds of (a) to (m) described above may be used alone or incombination of two or more kinds thereof for these photopolymerizationinitiators.

As preferred examples of (a) the carbonyl compound, (b) theacylphosphine oxide compound, and (e) the thio compound, compoundshaving a benzophenone skeleton or a thioxanthone skeleton described in“RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY,” J. P. FOUASSIER,J. F. RABEK (1993), pp. 77 to 117 are exemplified.

More preferred examples thereof include an α-thiobenzophenone compounddescribed in JP1972-6416B (JP-S47-6416B), a benzoin ether compounddescribed in JP1972-3981B (JP-S47-3981B), an α-substituted benzoincompound described in JP1972-22326B (JP-S47-22326B), a benzoinderivative described in JP1972-23664B (JP-S47-23664B), aroyl phosphonateester described in JP1982-30704B (JP-S52-30704B), dialkoxybenzophenonedescribed in JP1985-26483B (JP-S60-26483B), benzoin ethers described inJP1985-26403B (JP-S60-26403B) and JP1987-81345B (JP-S62-81345B),α-aminobenzophenones described in JP1989-34242B (JP-H01-3424B), U.S.Pat. No. 4,318,791A pamphlet, and EP0284561A1,p-di(dimethylaminobenzoyl)benzene described in JP1990-211452A(JP-H02-211452A), thio-substituted aromatic ketone described inJP1986-194062A (JP-S61-194062A), acylphosphine sulfide described inJP1990-9597B (JP-H02-9597B), acyl phosphine described in JP1990-9596B(JP-H02-9597B), thioxanthones described in JP1988-61950B(JP-S63-61950B), and coumarins described in JP1984-42864B(JP-S59-42864B). Moreover, polymerization initiators described inJP2008-105379A and JP2009-114290A are also preferable.

Among these photopolymerization initiators, (a) the carbonyl compound or(b) the acylphosphine oxide compound is more preferable and specificexamples thereof include bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (for example, IRGACURE (registered trademark) 819, manufactured byBASF Japan Ltd.),2-(dimethylamine)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (forexample, IRGACURE (registered trademark) 369, manufactured by BASF JapanLtd.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (forexample, IRGACURE (registered trademark) 907, manufactured by BASF JapanLtd.), 1-hydroxy-cyclohexyl-phenyl-ketone (for example, IRGACURE(registered trademark) 184, manufactured by BASF Japan Ltd.), and2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (for example, DAROCUR(registered trademark) TPO and LUCIRIN (registered trademark) TPO (bothmanufactured by BASF Japan Ltd.)).

Among these, from the viewpoints of improving the sensitivity and thecompatibility with LED light, as the photopolymerization initiator, (b)the acylphosphine oxide compound is preferable and a monoacylphosphineoxide compound (particularly preferably,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or a bisacyl phosphineoxide compound (particularly preferably,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) is more preferable.

In a case where the photosensitive composition of the present inventioncontains a photopolymerization initiator, the content of thephotopolymerization initiator is preferably in a range of 1.0% by massto 25.0% by mass, more preferably in a range of 2.0% by mass to 20.0% bymass, and still more preferably in a range of 3.0% by mass to 15.0% bymass based on the total amount of the photosensitive composition.

<Sensitizer>

From the viewpoint of improving the sensitivity, the photosensitivecomposition of the present invention can contain a sensitizer.

Particularly, in a case where LED light is used for curing a film, it ispreferable that the photosensitive composition of the present inventioncontains the above-described photopolymerization initiator and asensitizer.

In a case where the photosensitive composition of the present inventioncontains a sensitizer, only one kind or two or more kinds of sensitizersmay be contained.

A sensitizer is a substance that absorbs specific active energy rays andenters an electronically-excited state. A sensitizer having entered inan electronically-excited state is brought into a contact with aphotopolymerization initiator and causes actions of electron transfer,energy transfer, heat generation, and the like. In this manner, chemicalchange in the photopolymerization initiator, that is, decomposition orgeneration of a radical, an acid, or a base is promoted.

Examples of the sensitizer include a benzophenone (BP), a thioxanthone,isopropylthioxanthone (ITX), ethyl 4-(dimethylamino)benzoate (EDB),anthraquinone, a 3-acyl coumarin derivative, terphenyl, styryl ketone,3-(aroylmethylene)thiazoline, camphorquinone, eosin, rhodamine, anderythrosine.

Moreover, a compound represented by Formula (i) which is described inJP2010-24276A or a compound represented by Formula (I) which isdescribed in JP1994-107718A (JP-H06-107718A) can be suitably used as asensitizer.

Among the sensitizers described above, from the viewpoint ofcompatibility with LED light and reactivity with a photopolymerizationinitiator, at least one selected from thioxanthone,isopropylthioxanthone, ethyl 4-(dimethylamino)benzoate, and benzophenoneis preferable.

In a case where the photosensitive composition of the present inventioncontains a sensitizer, the content of the sensitizer is preferably in arange of 0.5% by mass to 10% by mass, more preferably in a range of 1.0%by mass to 7.0% by mass, and particularly preferably 2.0% by mass to6.0% by mass.

<Surfactant>

The photosensitive composition of the present invention may contain asurfactant.

As a surfactant, surfactants described in JP1987-173463A(JP-S62-173463A) and JP1987-183457A (JP-S62-183457A) can be exemplified.Examples thereof include anionic surfactants such as dialkylsulfosuccinate, alkyl naphthalene sulfonate, and fatty acid salts;nonionic surfactants such as polyoxyethylene alkyl ether,polyoxyethylene alkyl allyl ether, acetylene glycol, apolyoxyethylene.polyoxypropylene block copolymer and siloxanes such asmodified polydimethylsiloxane; cationic surfactants such as alkylaminesalts and quaternary ammonium salts; and betaine-based surfactants suchas carbobetaine and sulfobetaine.

Further, an organic fluoro compound which does not include apolymerizable group may be used instead of a surfactant. It ispreferable that the organic fluoro compound is hydrophobic. As theorganic fluoro compound, for example, a fluorine-containing surfactant,an oily fluorine-containing compound (for example, fluorine oil), asolid-like fluorine compound resin (for example, a tetrafluoroethyleneresin), and compounds described in JP1982-9053B (JP-S57-9053B) (sections8 to 17) and JP1987-135826B (JP-S62-135826B) are exemplified.

In a case where the photosensitive composition of the present inventioncontains a surfactant, the content of the surfactant is preferably in arange of 0.01% by mass to 5.0% by mass, more preferably in a range of0.1% by mass to 3.0% by mass, and particularly preferably in a range of0.3% by mass to 2.0% by mass based on the total amount of thephotosensitive composition.

(Polymerization Inhibitor)

The photosensitive composition of the present invention may contain apolymerization inhibitor.

Examples of the polymerization inhibitor include p-methoxyphenol,quinones (such as hydroquinone, benzoquinone, and methoxybenzoquinone),phenothiazine, catechols, alkylphenols (such as dibutyl hydroxy toluene(BHT)), alkyl bisphenols, zinc dimethyldithiocarbamate, copperdimethyldithiocarbamate, copper dibutyldithiocarbamate, coppersalicylate, thiodipropionic acid esters, mercaptobenzimidazole,phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO),2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL), cupferron Al,and tris(N-nitroso-N-phenylhydroxylamine)aluminum salts.

Among these, at least one selected from p-methoxyphenol, catechols,quinones, alkylphenols, TEMPO, TEMPOL, cupferron Al, andtris(N-nitroso-N-phenylhydroxyamine)aluminum salts is preferable and atleast one selected from p-methoxyphenol, hydroquinone, benzoquinone,BHT, TEMPO, TEMPOL, cupferron Al, andtris(N-nitroso-N-phenylhydroxyamine)aluminum salts is more preferable.

In a case where the photosensitive composition of the present inventioncontains a polymerization inhibitor, the content of the polymerizationinitiator is preferably in a range of 0.01% by mass to 2.0% by mass,more preferably in a range of 0.02% by mass to 1.0% by mass, andparticularly preferably in a range of 0.03% by mass to 0.5% by massbased on the total amount of the photosensitive composition.

<Solvent>

The photosensitive composition of the present invention may contain asolvent.

Examples of the solvent include ketone such as acetone, methyl ethylketone, or diethyl ketone; alcohol such as methanol, ethanol,2-propanol, 1-propanol, 1-butanol, or tert-butanol; a chlorinatedsolvent such as chloroform or methylene chloride; an aromatic solventsuch as benzene or toluene; an ester solvent such as ethyl acetate,butyl acetate, or isopropyl acetate; an ether solvent such as diethylether, tetrahydrofuran, or dioxane; and a glycol ether solvent such asethylene glycol monomethyl ether, ethylene glycol dimethyl ether.

In a case where the photosensitive composition of the present inventioncontains a solvent, from the viewpoint of reducing influence on asubstrate, the content of the solvent is preferably 5% by mass or less,more preferably in a range of 0.01% by mass to 5% by mass, andparticularly preferably in a range of 0.01% by mass to 3% by mass basedon the total amount of the photosensitive composition.

<Water>

The photosensitive composition of the present invention may contain aninfinitesimal amount of water within the range in which the effects ofthe present invention are not impaired.

However, from the viewpoint of more effectively obtaining the effects ofthe present invention, it is preferable that the photosensitivecomposition of the present invention is a non-aqueous photosensitivecomposition which does not substantially contain water. Specifically,the content of water is preferably 3% by mass or less, more preferably2% by mass or less, and particularly preferably 1% by mass or less basedon the total amount of the photosensitive composition.

<Colorant>

The photosensitive composition of the present invention may contain atleast one colorant.

The photosensitive composition containing a colorant can be suitablyused as an ink composition.

The colorant is not particularly limited and can be used by beingarbitrarily selected from known coloring materials such as pigments,water-soluble dyes, and dispersed dyes. Among these, in terms ofexcellent weather fastness and being rich in color reproducibility, itis more preferable that the photosensitive composition contains apigment.

The pigment is not particularly limited and can be appropriatelyselected according to the purpose thereof. Examples thereof includeknown organic pigments and inorganic pigments, resin particles dyed witha dye, commercially available pigment dispersions, and surface-treatedpigments (for example, pigments being dispersed in water, liquidcompounds, or insoluble resins as a dispersion medium and pigments whichare surface-treated by a resin or a pigment derivative).

Examples of the organic pigments and inorganic pigments include yellowpigments, red pigments, magenta pigments, blue pigments, cyan pigments,green pigments, orange pigments, purple pigments, brown pigments, blackpigments, and white pigments.

In a case where a pigment is used as a colorant, a pigment dispersantmay be used as necessary at the time of preparation of pigmentparticles.

The colorants such as pigments and pigment dispersants can beappropriately referred to known documents, for example, the paragraphs0152 to 0158 of JP2011-225848A and the paragraphs 0132 to 0149 ofJP2009-209352A.

In a case where the photosensitive composition of the present inventioncontains a colorant, the content of the colorant can be set to be in arange of 0.05% by mass to 20% by mass and is preferably in a range of0.2% by mass to 10% by mass based on the total amount of thephotosensitive composition.

<Other Components>

The photosensitive composition of the present invention may containcomponents other than the components described above.

Examples of the other components include an ultraviolet absorber, aco-sensitizer, an antioxidant, a fading inhibitor, and a conductivesalt.

Other components can be appropriately referred to known documents ofJP2011-225848A, JP2009-209352A, and the like.

<Preferable Physical Properties>

The viscosity of the photosensitive composition of the present inventionis not particularly limited.

The viscosity of the photosensitive composition of the present inventionat 25° C. is preferably in a range of 10 mPa·s to 50 mPa·s, morepreferably in a range of 10 mPa·s to 30 mPa·s, and still more preferablyin a range of 10 mPa·s to 25 mPa·s. The viscosity of the photosensitivecomposition can be adjusted by, for example, adjusting the compositionalratios of respective components to be contained.

The viscosity mentioned here is a value measured using a viscometer“VISCOMETER RE-85L” (manufactured by TOKI SANGYO CO., LTD.).

In a case where the viscosity of the photosensitive composition is inthe above-described preferable range, the jetting stability can befurther improved particularly in the case where the photosensitivecomposition is used as an ink composition.

The surface tension of the photosensitive composition of the presentinvention is not particularly limited.

The surface tension of the photosensitive composition of the presentinvention at 30° C. is preferably in a range of 20 mN/m to 30 mN/m andmore preferably in a range of 23 mN/m to 28 mN/m. In a case where a filmis formed on various substrates such as polyolefin, PET, coated paper,and uncoated paper, the surface tension thereof is preferably 30 mN/m orless in terms of wettability and preferably 20 mN/m or greater in termsof suppression of bleeding and permeability.

The surface tension mentioned here is a value measured using a surfacetensiometer DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).

[Image Forming Method]

An image forming method of the present embodiment includes anapplication process of applying an ink composition which is thephotosensitive composition of the present invention onto a recordingmedium according to an ink-jet method; and an irradiation process ofirradiating the ink composition applied onto the recording medium withactive energy rays.

According to the image forming method of the present embodiment, it ispossible to form an image having excellent hardness and adhesiveness toa recording medium. Further, the formed image is also excellent inblocking resistance.

Moreover, the image forming method of the present embodiment is alsoexcellent in storage stability and jetting stability of the inkcomposition.

(Application Process)

The application process is a process of applying the ink compositionwhich is the photosensitive composition of the present invention onto arecording medium.

As the mode of applying the ink composition onto a recording medium, amode of applying the ink composition onto a recording medium accordingto an ink-jet method is particularly preferable.

Substrates exemplified as the “substrates for forming a film” describedabove can be used as the recording medium.

Application of the ink composition according to the ink-jet method canbe performed using a known ink jet recording device.

The ink jet recording device is not particularly limited and a known inkjet recording device which can achieve the target resolution can bearbitrarily selected and used. That is, in a case of known ink jetrecording devices including commercially available products, it ispossible to perform jetting of an ink composition to a recording mediumaccording to the image forming method.

Examples of the ink jet recording device include devices including anink supply system, a temperature sensor, and heating means.

The ink supply system is formed of an original tank including an inkcomposition, a supply pipe, an ink supply tank immediately front of anink-jet head, a filter, and a piezoelectric ink-jet head. Thepiezoelectric ink-jet head can drive multi-size dots of preferably in arange of 1 pl to 100 pl and more preferably in a range of 8 pl to 30 plso as to be jetted with the resolution of preferably in a range of 320dpi×320 dpi (dot per inch) to 4000 dpi×4000 dpi (dot per inch), morepreferably in a range of 400 dpi×400 dpi to 1600 dpi×1600 dpi, and stillmore preferably in a range of 720 dpi×720 dpi to 1600 dpi×1600 dpi. Inaddition, “dpi” indicates the number of dots per 2.54 cm (1 inch).

(Irradiation Process)

The irradiation process is a process of irradiating the ink compositionapplied onto a recording medium with active energy rays.

By irradiating the ink composition applied onto a recording medium withactive energy rays, it becomes possible that a polymerization reactionof the ink composition proceeds, an image is fixed, and the filmhardness of an image is improved.

Examples of the active energy rays which can be used in the irradiationprocess include ultraviolet rays (UV light), visible light, and electronbeams. Among these, UV light is preferable.

The peak wavelength of the active energy rays (light) is preferably in arange of 200 nm to 405 nm, more preferably in a range of 220 nm to 390nm, and still more preferably in a range of 220 nm to 385 nm.

Further, the peak wavelength thereof is also preferably in a range of200 nm to 310 nm and also preferably in a range of 200 nm to 280 nm.

The exposure surface illuminance at the time of irradiation with activeenergy rays (light) is, for example, in a range of 10 mW/cm² to 2000mW/cm² and preferably in a range of 20 mW/cm² to 1000 mW/cm².

As sources used to generate active energy rays (light), a mercury lamp,a metal halide lamp, a UV fluorescent lamp, gas laser, and solid-statelaser are widely known.

Further, replacement of the light sources exemplified above with asemiconductor UV light emitting device is industrially andenvironmentally highly useful.

Further, among semiconductor UV light emitting device, a light emittingdiode (LED) and a laser diode (LD) are small in size, long in servicelife, highly efficient, and at low cost, and thus the LED and the LD areexpected as light sources for active energy rays.

As the light sources, a metal halide lamp, an extra-high pressuremercury lamp, a high pressure mercury lamp, a medium pressure mercurylamp, a low pressure mercury lamp, an LED, and blue-violet laser arepreferable.

Among these, in a case where a sensitizer and a photopolymerizationinitiator are used in combination, an extra-high pressure mercury lampwhich is capable of irradiation with light at a wavelength of 365 nm,405 nm, or 436 nm, a high pressure mercury lamp which is capable ofirradiation with light at a wavelength of 365 nm, 405 nm, or 436 nm, oran LED which is capable of irradiation with light at a wavelength of 355nm, 365 nm, 385 nm, 395 nm, or 405 nm is more preferable; and an LEDwhich is capable of irradiation with light at a wavelength of 355 nm,365 nm, 385 nm, 395 nm, or 405 nm is most preferable.

In the irradiation process, the time for irradiating the ink compositionapplied onto a recording medium with active energy rays is in a range of0.01 seconds to 120 seconds and preferably in a range of 0.1 seconds to90 seconds.

As the irradiation conditions and the basic irradiation methods,similarly, irradiation conditions and irradiation methods disclosed inJP1985-132767A (JP-S60-132767A) can be used.

Specifically, as a method of irradiation with active energy rays, amethod in which irradiation with active energy rays is performed byproviding light sources on both sides of a head unit including a jettingdevice of an ink composition and scanning the head unit and lightsources using a so-called shuttle system or a method in whichirradiation with active energy rays is performed using another lightsource that is not driven is preferable.

It is preferable that the irradiation with active energy rays isperformed after a certain period of time (for example, in a range of0.01 seconds to 120 seconds and preferably in a range of 0.01 seconds to60 seconds) after the ink composition is impacted, heated, and thendried.

(Heating and Drying Process)

The image forming method may further include a heating and dryingprocess after the application process and before the irradiation processas needed.

Examples of the heating means are not particularly limited and include aheat drum, hot air, an infrared lamp, a heat oven, and heating using aheating plate.

The heating temperature is preferably 40° C. or higher, more preferablyin a range of 40° C. to 150° C., and still more preferably in a range of40° C. to 80° C.

Moreover, the heating time can be appropriately set in consideration ofthe composition of the ink composition and the printing speed.

The ink composition fixed by heating is optically fixed by beingirradiated with active energy rays in the irradiation process asnecessary. As described above, in the irradiation process, it ispreferable that the ink composition is fixed using UV light.

[Film Forming Method]

A film forming method of the present embodiment includes an applicationprocess of applying the photosensitive composition of the presentinvention onto a substrate; and an irradiation process of irradiatingthe photosensitive composition applied onto the substrate with activeenergy rays. According to the film forming method of the presentembodiment, a film having excellent hardness and adhesiveness to asubstrate can be formed. Further, the formed film is also excellent inblocking resistance.

Moreover, the film forming method of the present embodiment is excellentin storage stability of the photosensitive composition and alsoexcellent in jetting stability in a case where an ink composition isjetted from an ink jet head.

The film forming method of the present embodiment is the same as theimage forming method of the present embodiment except that the method ofapplying the photosensitive composition onto a substrate is not limitedto the ink-jet method and the preferable modes are the same as eachother.

The application of the photosensitive composition onto a substrate canbe performed by applying a known coating method or printing method otherthan the ink-jet method.

The application (coating) of the photosensitive composition according toa coating method can be performed using a coating device such as a barcoater, a roll coater, a slit coater, or a spin coater.

[Resin, Image, Film]

A resin of the present embodiment includes at least one structural unitC selected from the group consisting of units (1-1) to (1-8) and (2-1)and at least one structural unit D selected from the group consisting ofunits (3-3) to (3-5), (4-1) to (4-4), and (5-1) to (5-3).

The resin of the present embodiment is effective as a component of thephotosensitive composition described above.

The preferable mode of the resin of the present embodiment is the sameas the preferable mode of the specific resin in the above-describedphotosensitive composition.

For example, it is preferable that the resin of the present embodimentincludes a structural unit which is a unit (1-1) and at least onestructural unit selected from the group consisting of units (4-1) to(4-3), (5-1), and (5-2); more preferable that the resin of the presentembodiment includes a structural unit which is a unit (1-1) and at leastone structural unit selected from units (4-3) and (5-2); andparticularly preferable that the resin of the present embodimentincludes a structural unit which is a unit (1-1), a structural unitwhich is a unit (4-3), and a structural unit which is a unit (5-2).

The image of the present embodiment contains the resin of the presentembodiment. For this reason, the image of the present embodiment hasexcellent hardness and adhesiveness to a recording medium. Further, theimage of the present embodiment is also excellent in blockingresistance.

Moreover, the film of the present embodiment contains the resin of thepresent embodiment. For this reason, the film of the present embodimenthas excellent hardness and adhesiveness to a substrate. Further, thefilm of the present embodiment is also excellent in blocking resistance.

EXAMPLES

Hereinafter, the present invention will be described in detail withreference to examples, but the present invention is not limited to theexamples described below as long as it is within the gist of the presentinvention.

Hereinafter, the numbers at the bottom right of respective structuralunits of a resin (copolymer) indicate copolymerization ratios (% bymass).

[Synthesis of Resin]

<Synthesis of Resin Used in Example 1A>

A resin used in Example 1A (hereinafter, also referred to as a “resin(1A)”) was synthesized as follows.

99.91 g of methyl propylene glycol (reaction solvent) was weighed in a300 ml three-neck flask including a cooling pipe and was heated andstirred at 75° C. in a nitrogen stream. Apart from this, a mixedsolution prepared by mixing 66.61 g of methyl propylene glycol, 35 g ofpentamethyl piperidyl methacrylate (raw material monomer), 35 g ofphenoxy ethyl methacrylate (raw material monomer), 0.7275 g of V-601(dimethyl 2,2′-azobis(2-methylpropionate), initiator manufactured byWako Pure Chemical Industries, Ltd.), and 0.6394 g of dodecyl mercaptan(chain transfer agent) was added dropwise to the above-described flaskover two hours. After dropwise addition, the solution was heated at 75°C. for 4 hours, 0.09 g of V-601 (initiator) was added thereto, and thesolution was further stirred at 90° C. for 2 hours and then reacted.

The obtained reaction solution was allowed to be cooled, and the cooledreaction solution was poured into 2000 ml of water, re-precipitated,purified, and vacuum-dried.

As described before, approximately 60 g of a resin (1A) (weight-averagemolecular weight (Mw): 10000) having a structure shown below wasobtained.

<Synthesis of Resin Used in Example 25A>

A resin used in Example 25A (hereinafter, also referred to as a “resin(25A)”) was synthesized as follows. 100.4 g of methyl propylene glycolwas weighed in a 300 ml three-neck flask including a cooling pipe andwas heated and stirred at 75° C. in a nitrogen stream. Apart from this,a mixed solution prepared by mixing 66.93 g of methyl propylene glycol,35 g of pentamethyl piperidyl methacrylate (raw material monomer), 35 gof N-vinyl caprolactam (raw material monomer), 0.9157 g of V-601(initiator), and 0.8049 g of dodecyl mercaptan was added dropwise to theabove-described flask over two hours. After dropwise addition, thesolution was heated at 75° C. for 4 hours, 0.09 g of V-601 (initiator)was added thereto, and the solution was further stirred at 90° C. for 2hours and then reacted.

The obtained reaction solution was allowed to be cooled, and the cooledreaction solution was poured into 2000 ml of water, re-precipitated,purified, and vacuum-dried.

As described before, approximately 60 g of a resin (25A) (weight-averagemolecular weight (Mw): 10000) having a structure shown below wasobtained.

<Synthesis of Resin Used in Example 39A>

A resin used in Example 39A (hereinafter, also referred to as a “resin(39A)”) was synthesized as follows. 100.4 g of methyl propylene glycolwas weighed in a 300 ml three-neck flask including a cooling pipe andwas heated and stirred at 75° C. in a nitrogen stream. Apart from this,a mixed solution prepared by mixing 66.93 g of methyl propylene glycol,35 g of pentamethyl piperidyl methacrylate (raw material monomer), 21 gof N-vinyl caprolactam (raw material monomer), 14 g of acryloylmorpholine (raw material monomer), 0.9124 g of V-601 (initiator), and0.8020 g of dodecyl mercaptan was added dropwise to the above-describedflask over two hours. After dropwise addition, the solution was heatedat 75° C. for 4 hours, 0.09 g of V-601 (initiator) was added thereto,and the solution was further stirred at 90° C. for 2 hours and thenreacted.

The obtained reaction solution was allowed to be cooled, and the cooledreaction solution was poured into 2000 ml of water, re-precipitated,purified, and vacuum-dried.

As described before, approximately 60 g of a resin (39A) (weight-averagemolecular weight (Mw): 10000) having a structure shown below wasobtained.

Resins used in other examples described below were synthesized in thesame manner as those of the resin (1A), the resin (25A), and the resin(39A) by appropriately selecting the kind of raw material monomer andthe amount to be used.

The weight-average molecular weight (Mw) was adjusted by adjusting theamounts of V-601 (initiator) and dodecyl mercaptan.

Example 1A

<Preparation of Photosensitive Composition A (Based on MonofunctionalMonomer, Free from Sensitizer, and Free from Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition A was prepared.

The compositions of the photosensitive composition A is based on amonofunctional monomer (that is, a monofunctional radicallypolymerizable monomer, the same applies to hereinafter) and do not havea sensitizer nor a colorant.

—Compositions of Photosensitive Composition A (Based on MonofunctionalMonomer, Free from Sensitizer, and Free from Colorant)—

TMCHA (monofunctional monomer) described below 15.0% by mass  DCPA(monofunctional monomer) described below 15.0% by mass  IBOA(monofunctional monomer) described below 20.9% by mass  CTFA(monofunctional monomer) described below 23.0% by mass  PEA(monofunctional monomer) described below 10.0% by mass  CN964 (urethaneoligomer having polymerizable 2.0% by mass group, manufactured bySartomer Company) IRGACURE 819 (photopolymerization initiator 5.0% bymass manufactured by BASF Japan Ltd., acyl phosphine oxide compound,specifically, bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide)IRGACURE 184 (photopolymerization initiator 3.0% by mass manufactured byBASF Japan Ltd., carbonyl compound, specifically, 1-hydroxy-cyclohexyl-phenyl-ketone) FIRSTCURE ST-1 (polymerization inhibitor 0.1% by massmanufactured by Albemarle Corporation,tris(N-nitroso-N-phenylhydroxylamine)aluminum salts) BYK-UV3575(modified polydimethylsiloxane 1.0% by mass surfactant manufactured byBYK Chemie GmbH) Resin listed in Table 1 5.0% by mass

<Evaluation of Photosensitive Composition A>

Evaluation described below was performed using the photosensitivecomposition A.

The results are listed in Table 1.

(Adhesiveness of Cured Film)

The adhesiveness was evaluated respectively using a sample (PVC) forevaluation, a sample (A-PET) for evaluation, a sample (acryl) forevaluation, a sample (PC) for evaluation, and a sample (PS) forevaluation described below.

The sample (PVC) for evaluation was prepared in the following manner.

First, a polyvinyl chloride (PVC) sheet serving as a substrate wascoated with the photosensitive composition A obtained in theabove-described manner at a thickness of 12 μm using a K hand coater(bar No. 2, manufactured by RK Print Coat Instruments Ltd.), therebyobtaining a coating film. The obtained coating film was irradiated withUV light (ultraviolet rays) using a UV mini-conveyor apparatus CSOT(manufactured by GS Yuasa International Ltd.) for a test which wasequipped with an ozoneless metal halide lamp MAN250L and in which theconveyor speed was set to 9.0 m/min and the exposure intensity was setto 2.0 W/cm², and thus the coating film was cured, thereby obtaining acured film. In this manner, the sample (PVC) for evaluation wasobtained.

The sample (A-PET) for evaluation was prepared in the same manner asthat of the sample (PVC) for evaluation except that the substrate waschanged into amorphous polyethylene terephthalate (A-PET) sheet.

The sample (acryl) for evaluation was prepared in the same manner asthat of the sample (PVC) for evaluation except that the substrate waschanged into an acrylic resin sheet.

The sample (PC) for evaluation was prepared in the same manner as thatof the sample (PVC) for evaluation except that the substrate was changedinto a polycarbonate (PC) sheet.

The sample (PS) for evaluation was prepared in the same manner as thatof the sample (PVC) for evaluation except that the substrate was changedinto a polystyrene (PS) sheet.

Here, the following sheets were respectively used as the PVC sheet, theA-PET sheet, the acrylic resin sheet, the PC sheet, and the PS sheet.

-   -   PVC sheet: “AVERY (registered trademark) 400 GLOSS WHITE        PERMANENT” (manufactured by Avery Dennison Corporation)    -   A-PET sheet: “A-PET” (amorphous polyethylene terephthalate        sheet) (manufactured by Takiron Co., Ltd.)    -   Acrylic resin sheet: “Acryace (registered trademark) UV”        (manufactured by JSP Corporation)    -   PC sheet: “PC1600-2” (manufactured by Takiron Co., Ltd.)    -   PS sheet: “falcon hi impact polystyrene” (manufactured by Robert        Horne Group Ltd.)

A cross hatch test was performed on cured films of respective samplesfor evaluation in conformity with ISO2409 (cross-cut method), andevaluation was performed based on the following evaluation criteria.

In the cross hatch test, the cut interval was set to 1 mm and 25 piecesof square lattices having a dimension of 1 mm² were formed.

In the following evaluation criteria, 0 and 1 are acceptable forpractical use.

In the following evaluation criteria, a percentage (%) of a lattice tobe peeled off is a value acquired by the following equation. The totalnumber of lattices acquired by the following equation is 25.Percentage (%) of lattice to be peeled off=[(number of lattices beingpeeled off)/(total number of lattices)]×100

—Evaluation Criteria of Adhesiveness of Cured Film—

0: The percentage (%) of a lattice to be peeled off was 0%.

1: The percentage (%) of a lattice to be peeled off was greater than 0%to 5% or less.

2: The percentage (%) of a lattice to be peeled off was greater than 5%to 15% or less.

3: The percentage (%) of a lattice to be peeled off was greater than 15%to 35% or less.

4: The percentage (%) of a lattice to be peeled off was greater than 35%to 65% or less.

5: The percentage (%) of a lattice to be peeled off was greater than65%.

(Pencil Hardness of Cured Film)

The evaluation of pencil hardness of the cured film was performed usingthe above-described sample (PVC) for evaluation.

The pencil hardness test was performed on the cured film of the sample(PVC) for evaluation using UNI (registered trademark, manufactured byMITSUBISHI PENCIL CO., LTD.) as a pencil in conformity with JISK5600-5-4 (1999).

In the test results, the acceptable range of pencil hardness is HB orhigher and preferably H or higher. There is a possibility that a printedmatter whose pencil hardness is B or lower is damaged at the time ofhandling the printed matter, which is not preferable.

(Blocking Resistance of Cured Film)

The evaluation of blocking resistance of the cured film was performedusing the above-described sample (PVC) for evaluation.

The sample (PVC) for evaluation was cut into a size of 20 mm×20 mm andthis was used as an evaluation sample. Two evaluation samples wereprepared.

Next, two evaluation samples were overlapped each other such that thecured films were brought into contact with each other, and a load of 10N was applied to a direction in which two evaluation samples werepressed against each other for 10 seconds, and then the evaluationsamples were peeled off.

Subsequently, each of the cured films of the two evaluation samples wasobserved, the presence or absence of traces in which the cured filmswere adhered to each other and the degree of adhesion in traces wasvisually observed, and then the blocking resistance of the cured filmswas evaluated based on the following evaluation criteria.

The results are listed in Table 1.

—Evaluation Criteria of Blocking Resistance of Cured Film—

5: Traces in which cured films were adhered to each other were not foundand the blocking resistance of a cured film was markedly excellent.

4: Traces in which cured films were adhered to each other were found ina range of greater than 0% to less than 3% of the entire area of a curedfilm, but the blocking resistance of the cured film was not problematicfor practical use.

3: Traces in which cured films were adhered to each other were found ina range of 3% to less than 10% of the entire area of a cured film, butthe blocking resistance of the cured film was within the acceptablerange for practical use.

2: Traces in which cured films were adhered to each other were found ina range of 10% to less than 50% of the entire area of a cured film, andthe blocking resistance of the cured film was out of the acceptablerange for practical use.

1: Traces in which cured films were adhered to each other were found in50% or greater of the entire area of a cured film, and the blockingresistance of the cured film was extremely poor.

(Jetting Stability of Photosensitive Composition A)

The jetting stability of the photosensitive composition A (ink) wasevaluated using a commercially available ink jet recording device(LuxelJet (registered trademark) UV3600GT/XT: trade name, manufacturedby Fujifilm Holdings Corporation) including a piezoelectric ink jettinghead, a polyethylene terephthalate (PET) film (manufactured by TorayIndustries, Inc.) as a recording medium (substrate), and thephotosensitive composition A as an ink according to the followingmethod.

A process of forming a 100% solid image by jetting the photosensitivecomposition A (ink) onto the PET film under the following jettingconditions using the ink jet recording device and irradiating impactedink with UV light (irradiation dose: 1000 mW/cm²) was continuouslyperformed for 60 minutes.

The number of nozzles with ink clogging (nozzle loss) being generated ina case where the process was continuously performed for 60 minutes andthe photosensitive composition was jetted was acquired, and evaluationwas performed based on the following evaluation criteria.

In the following evaluation criteria, 5 or 4 are acceptable forpractical use.

—Jetting Conditions—

-   -   Number of channels: 318/head    -   Drive frequency: 4.8 kHz/dot    -   Ink drops: 7 drops, 42 pl    -   Temperature of head nozzle: 45° C.

—Jetting Stability of Photosensitive Composition A—

5: The nozzle loss is 0 to less than 2.

4: The nozzle loss is 2 to less than 5.

3: The nozzle loss is 5 to less than 7.

2: The nozzle loss is 7 to less than 10.

1: The nozzle loss is 10 or greater.

(Storage of Photosensitive Composition A)

The photosensitive composition A (50 mL) was put into a 50 mL glassbottle, and the bottle was covered and allowed to stand for 4 hoursunder a condition of a thermostatic bath (60° C.). The storage stabilityof the photosensitive composition A was evaluated based on the followingevaluation criteria by measuring the viscosity of the photosensitivecomposition A before and after the composition was allowed to stand andacquiring an increase rate of the viscosity after the composition wasallowed to stand with respect to the viscosity before the compositionwas allowed to stand. In the following evaluation criteria, 5 or 4 isacceptable for practical use.

Moreover, the viscosity of the photosensitive composition A was measuredusing a VISCOMETER RE-85L (manufactured by TOKI SANGYO CO., LTD.) as aviscometer under a liquid temperature condition of 25° C.

The results are listed in Table 1.

—Evaluation Criteria of Storage Stability of Photosensitive CompositionA—

5: The increase rate of the viscosity after the composition was allowedto stand with respect to the viscosity before the composition wasallowed to stand is less than 10%.

4: The increase rate of the viscosity after the composition was allowedto stand with respect to the viscosity before the composition wasallowed to stand is 10% to less than 20%.

3: The increase rate of the viscosity after the composition was allowedto stand with respect to the viscosity before the composition wasallowed to stand is 20% to less than 30%.

2: The increase rate of the viscosity after the composition was allowedto stand with respect to the viscosity before the composition wasallowed to stand is 30% to less than 40%.

1: The increase rate of the viscosity after the composition was allowedto stand with respect to the viscosity before the composition wasallowed to stand is 40% or greater.

Examples 2A to 51A

Operations which were the same as those in Example 1A were performedexcept that at least one of the kind of resin (the kind of structuralunit, the copolymerization ratio, and Mw) in the compositions of thephotosensitive composition A and the content of the resin based on thetotal amount of the composition (hereinafter, also simply referred to asthe “content of a resin”) was changed as listed in Table 1.

The results are listed in Table 1.

In the case of an example in which the content of the resin was changed,the total amount of the resin and monomers was set to be the same as inExample 1A by setting the compositional ratio of monomers to be constantand changing the total amount of the monomers.

Comparative Examples 1A to 5A

In the compositions of the photosensitive composition A, operationswhich were the same as those in Example 1A were performed except thatthe kind of resin was changed as listed in Table 1.

The results are listed in Table 1.

In Comparative Examples 1A to 5A, the structures of comparative resins ato d and a comparative compound e are as follows. In the comparativeresins a to d, the numbers at the bottom right of respective structuralunits indicate copolymerization mass ratios. Further, the Mws of thecomparative resins a to d are respectively as listed in Table 1.

Here, the comparative resins a, b, and c are respectively shown inspecific examples (A-24), (A-25), and (A-7) described in the paragraphs0100 and 0103 of JP2011-225848A.

The comparative resin d is PA-5 described in the paragraph 0219 ofJP2009-139852A.

The comparative compound e is ADK STAB LA-52 (manufactured by ADEKACORPORATION).

TABLE 1 Photosensitive composition A (based on monofunctional monomer,free from sensitizer, and free from colorant) Resin Content Copoly-based Struc- merization on total Evaluation results tural Structuralratio amount of Pencil Adhesiveness unit A unit B (% by mass)composition hard- Blocking A- Storage Jetting a1 b1 b2 a1 b1 b2 Mw (% bymass) ness resistance PVC PET Acryl PC PS stability stability Example 1A(1-1) (3-1) 50 50 0 10000 5.0 F 4 0 1 1 0 1 5 5 Example 2A (1-1) (3-2)50 50 0 10000 5.0 F 4 0 1 1 0 1 5 5 Example 3A (1-2) (5-2) 50 50 0 100005.0 F 5 0 0 0 0 0 5 5 Example 4A (1-3) (5-2) 50 50 0 10000 5.0 F 4 0 0 00 0 5 5 Example 5A (1-4) (5-2) 50 50 0 10000 5.0 F 5 0 0 0 0 0 5 5Example 6A (1-5) (5-2) 50 50 0 10000 5.0 F 4 0 0 0 0 0 5 5 Example 7A(1-6) (5-2) 50 50 0 10000 5.0 F 4 0 0 0 0 0 5 5 Example 8A (1-7) (5-2)50 50 0 10000 5.0 F 4 0 0 0 0 0 5 5 Example 9A (1-8) (5-2) 50 50 0 100005.0 F 5 0 0 0 0 0 5 5 Example 10A (2-1) (5-2) 50 50 0 10000 5.0 F 4 0 00 0 0 5 5 Example 11A (1-1) (4-4) 50 50 0 10000 5.0 F 5 0 1 0 0 1 5 5Example 12A (1-1) (5-3) 50 50 0 10000 5.0 F 5 0 1 0 0 1 5 5 Example 13A(1-1) (3-3) 50 50 0 10000 5.0 F 5 0 1 0 0 1 5 5 Example 14A (1-1) (3-4)50 50 0 10000 5.0 F 5 0 1 0 0 1 5 5 Example 15A (1-1) (3-5) 50 50 010000 5.0 F 5 0 1 0 0 1 5 5 Example 16A (1-1) (4-1) 50 50 0 10000 5.0 H5 0 1 0 0 0 5 5 Example 17A (1-1) (4-1) 40 60 0 10000 5.0 H 5 0 1 0 0 05 5 Example 18A (1-1) (4-1) 60 40 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example19A (1-1) (4-2) 50 50 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example 20A (1-1)(4-2) 70 30 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example 21A (1-1) (4-2) 30 700 10000 5.0 H 5 0 1 0 0 0 5 5 Example 22A (1-1) (5-2) 20 80 0 10000 5.0H 4 0 0 0 0 0 5 5 Example 23A (1-1) (5-2) 10 90 0 10000 5.0 H 4 0 1 1 00 5 5 Example 24A (1-1) (5-2) 30 70 0 10000 5.0 H 5 0 0 0 0 0 5 5Example 25A (1-1) (5-2) 50 50 0 10000 5.0 H 5 0 0 0 0 0 5 5 Example 26A(1-1) (5-2) 70 30 0 10000 5.0 H 5 0 0 0 0 0 5 5 Example 27A (1-1) (5-2)80 20 0 10000 5.0 H 5 0 1 1 0 0 5 5 Example 28A (1-1) (5-2) 90 10 010000 5.0 H 5 0 1 1 1 0 5 5 Example 29A (1-1) (5-1) 20 80 0 10000 5.0 H4 0 1 0 0 1 5 5 Example 30A (1-1) (5-1) 30 70 0 10000 5.0 H 5 0 1 0 0 05 5 Example 31A (1-1) (5-1) 50 50 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example32A (1-1) (5-1) 70 30 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example 33A (1-1)(5-1) 80 20 0 10000 5.0 H 5 0 1 1 0 0 5 5 Example 34A (1-1) (4-3) 20 800 10000 5.0 H 4 0 0 0 0 1 5 5 Example 35A (1-1) (4-3) 30 70 0 10000 5.0H 5 0 0 0 0 0 5 5 Example 36A (1-1) (4-3) 50 50 0 10000 5.0 H 5 0 0 0 00 5 5 Example 37A (1-1) (4-3) 70 30 0 10000 5.0 H 5 0 0 0 0 0 5 5Example 38A (1-1) (4-3) 80 20 0 10000 5.0 H 5 0 1 1 0 0 5 5 Example 39A(1-1) (5-2) (4-3) 50 30 20 10000 5.0 H 5 0 0 0 0 0 5 5 Example 40A (1-1)(5-2) (4-3) 40 40 20 10000 5.0 H 5 0 0 0 0 0 5 5 Example 41A (1-1) (5-2)(4-3) 60 20 20 10000 5.0 H 5 0 0 0 0 0 5 5 Example 42A (1-1) (5-2) 50 500 5000 5.0 H 5 0 0 0 0 0 5 5 Example 43A (1-1) (5-2) 50 50 0 25000 5.0 H5 0 0 0 0 0 5 5 Example 44A (1-1) (5-2) 50 50 0 40000 5.0 H 5 0 0 0 0 05 5 Example 45A (1-1) (4-3) 50 50 0 3000 5.0 H 5 0 0 0 0 0 5 5 Example46A (1-1) (4-3) 50 50 0 17000 5.0 H 5 0 0 0 0 0 5 5 Example 47A (1-1)(4-3) 50 50 0 50000 5.0 H 5 0 0 0 0 0 5 5 Example 48A (1-1) (5-2) 50 500 10000 0.5 F 5 0 0 0 0 0 5 5 Example 49A (1-1) (5-2) 50 50 0 10000 2.0H 5 0 0 0 0 0 5 5 Example 50A (1-1) (5-2) 50 50 0 10000 7.0 H 5 0 0 0 00 5 5 Example 51A (1-1) (5-2) 50 50 0 10000 10.0 H 5 0 0 0 0 0 5 4Comparative Comparative resin a 33000 5.0 3B 2 3 4 5 5 5 1 2 Example 1AComparative Comparative resin b 15000 5.0 2B 3 3 4 4 4 4 1 1 Example 2AComparative Comparative resin c 12000 5.0 3B 2 3 4 4 4 4 1 3 Example 3AComparative Comparative resin d 60000 5.0 3B 1 3 5 5 5 5 2 1 Example 4AComparative Comparative compound e 5.0 2B 2 4 5 5 5 5 4 4 Example 5A

In the columns of “Resin” in Table 1, “al” indicates a structural unitincluded in the range of the structural unit A, “b1” and “b2” indicate astructural unit included in the range of the structural unit B. Further,the symbols of “(1-1)” and the like in respective examples indicate theunit (1-1) and the like.

The same applies to Tables 2 to 6.

As listed in Table 1, the photosensitive composition A in Examples 1A to51A which includes a resin having the structural unit A and thestructural unit B was excellent in storage stability and jettingstability (hereinafter, also referred to as “storage stability and thelike”) and the cured films formed in these examples were excellent inpencil hardness, adhesiveness to a substrate, and blocking resistance(hereinafter, also referred to as “pencil hardness, adhesiveness, andthe like”).

With respect to the respective examples, the photosensitive compositionsin comparative examples (Comparative Examples 1A, 3A, and 4A) which didnot include the structural unit A and for which the comparative resinsa, c, and d were used were inferior in storage stability and the likeand also inferior in pencil hardness of a cured film, adhesiveness ofthe cured film to a substrate, and the like. Similarly, thephotosensitive composition in the comparative example (ComparativeExample 2A) which did not include the structural unit B and for whichthe comparative resin b was used were inferior in storage stability andthe like and also inferior in pencil hardness of a cured film,adhesiveness of the cured film, and the like.

Moreover, the photosensitive composition in Comparative Example 5A,which did not use a resin but used the comparative compound e, wasinferior in pencil hardness of a cured film, adhesiveness of the curedfilm, and the like.

Further, from the results of Examples 3A to 9A and 25A, from theviewpoint of the blocking resistance of a cured film, it is understoodthat the units (1-1), (1-2), (1-4), and (1-8) are preferable as thestructural unit A. Among these, from the viewpoints of the hardness andthe blocking resistance of a cured film, it is understood that the unit(1-1) is particularly preferable as the structural unit A.

Further, from the results of Examples 1A to 16A, 25A, 31A, and 36A, fromthe viewpoints of the blocking resistance and the adhesiveness of acured film, it is understood that the units (3-3) to (3-5), (4-1) to(4-4), and (5-1) to (5-3) are preferable as the structural unit B. Amongthese, from the viewpoints of the hardness, the blocking resistance, andthe adhesiveness of a cured film, it is understood that the units (4-1)to (4-3), (5-1), and (5-2) are more preferable as the structural unit B.

Moreover, from the results of Examples 22A to 38A, from the viewpointsof the blocking resistance and the adhesiveness of a cured film, it isunderstood that the proportion of the structural unit A in the totalamount of the structural unit A and the structural unit B is preferablyin a range of 20% by mass to 80% by mass and particularly preferably ina range of 30% by mass to 70% by mass.

In addition, from the results of Examples 48A to 51A, it is understoodthat the content of a resin based on the total amount of the compositionis preferably 1.0% by mass or greater from the viewpoints of the pencilhardness of a film and is preferably 9.0% by mass or less from theviewpoint of the jetting stability.

Example 1B

<Preparation of Photosensitive Composition B (Based on MonofunctionalMonomer, Having Sensitizer, and Free from Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition B was prepared.

The compositions of the photosensitive composition B are based on amonofunctional monomer, have a sensitizer, and do not have a colorant.

—Compositions of Photosensitive Composition B (Based on MonofunctionalMonomer, Having Sensitizer, and Free from Colorant)—

IBOA (monofunctional monomer) described below 30.0% by mass  CTFA(monofunctional monomer) described below 30.0% by mass  PEA(monofunctional monomer) described below 19.9% by mass  CN964 (urethaneoligomer having polymerizable group, manufactured by Sartomer 2.0% bymass Company) IRGACURE 819 (photopolymerization initiator manufacturedby BASF Japan Ltd., 5.0% by mass acyl phosphine oxide compound,specifically, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide)IRGACURE 184 (photopolymerization initiator manufactured by BASF JapanLtd., 3.0% by mass carbonyl compound, specifically,1-hydroxy-cyclohexyl-phenyl-ketone) ITX (sensitizer,2-isopropylthioxanthone) 1.0% by mass BP (sensitizer, benzophenone) 2.0%by mass EDB (sensitizer, ethyl 4-(dimethylamino)benzoate) 1.0% by massFIRSTCURE ST-1 (polymerization inhibitor manufactured by AlbemarleCorporation, 0.1% by mass tris(N-nitroso-N-phenylhydroxylamine)aluminumsalts) BYK-UV3575 (modified polydimethylsiloxane surfactant manufacturedby BYK 1.0% by mass Chemie GmbH) Resin listed in Table 2 5.0% by mass

<Evaluation of Photosensitive Composition B>

Evaluation was performed in the same manner as in Example 1A except thatthe photosensitive composition B was used in place of the photosensitivecomposition A and the exposure device and the exposure conditions werechanged as shown below.

The results are listed in Table 2.

In the evaluation of the photosensitive composition B, a 385 nm UV-LEDirradiator (manufactured by CCS Inc.) for a test was used as an exposuredevice and an exposure energy of 300 mJ/cm² was set as the exposurecondition.

Examples 2B to 18B

Operations which were the same as those in Example 1B were performedexcept that the kind of resin (the kind of structural unit, thecopolymerization ratio, and Mw) in the compositions of thephotosensitive composition B was changed as listed in Table 2.

The results are listed in Table 2.

Comparative Examples 1B to 5B

Operations which were the same as those in Example 1B were performedexcept that the kind of resin in the compositions of the photosensitivecomposition B was changed as listed in Table 2.

The results are listed in Table 2.

In Comparative Examples 1B to 5B, the comparative resins a to d and thecomparative compound e are as described above.

TABLE 2 Photosensitive composition B (based on monofunctional monomer,having sensitizer, and free from colorant) Resin Content Copoly- basedon Struc- merization total amount Evaluation results tural Structuralratio of Pencil Adhesiveness unit A unit B (% by mass) composition hard-Blocking A- Storage Jetting a1 b1 b2 a1 b1 b2 Mw (% by mass) nessresistance PVC PET Acryl PC PS stability stability Example 1B (1-1)(3-1) 50 50 0 10000 5.0 F 4 0 1 1 0 1 5 5 Example 2B (1-1) (3-3) 50 50 010000 5.0 F 4 0 1 0 0 1 5 5 Example 3B (1-1) (3-4) 50 50 0 10000 5.0 F 50 1 0 0 1 5 5 Example 4B (1-1) (3-5) 50 50 0 10000 5.0 F 5 0 1 0 0 1 5 5Example 5B (1-1) (4-1) 50 50 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example 6B(1-1) (4-2) 50 50 0 10000 5.0 H 4 0 1 0 0 0 5 5 Example 7B (1-1) (5-2)30 70 0 10000 5.0 H 5 0 0 0 0 0 5 5 Example 8B (1-1) (5-2) 50 50 0 100005.0 H 5 0 0 0 0 0 5 5 Example 9B (1-1) (5-2) 70 30 0 10000 5.0 H 5 0 0 00 0 5 5 Example 10B (1-1) (4-1) 50 50 0 10000 5.0 H 5 0 1 0 0 0 5 5Example 11B (1-1) (4-1) 70 30 0 10000 5.0 H 5 0 1 0 0 0 5 5 Example 12B(1-1) (4-3) 50 50 0 10000 5.0 H 5 0 0 0 0 0 5 5 Example 13B (1-1) (4-3)70 30 0 10000 5.0 H 5 0 0 0 0 0 5 5 Example 14B (1-1) (5-2) (4-3) 50 3020 10000 5.0 H 5 0 0 0 0 0 5 5 Example 15B (1-1) (5-2) 50 50 0 5000 5.0H 5 0 0 0 0 0 5 5 Example 16B (1-1) (5-2) 50 50 0 25000 5.0 H 5 0 0 0 00 5 5 Example 17B (1-1) (4-3) 50 50 0 3000 5.0 H 5 0 0 0 0 0 5 5 Example18B (1-1) (4-3) 50 50 0 17000 5.0 H 5 0 0 0 0 0 5 5 ComparativeComparative resin a 33000 5.0 3B 2 3 4 5 5 5 1 2 Example 1B ComparativeComparative resin b 15000 5.0 2B 3 3 4 4 4 4 1 1 Example 2B ComparativeComparative resin c 12000 5.0 3B 2 3 4 4 4 4 1 3 Example 3B ComparativeComparative resin d 60000 5.0 3B 1 3 5 5 5 5 2 1 Example 4B ComparativeComparative compound e 5.0 2B 2 4 5 5 5 5 4 4 Example 5B

As listed in Table 2, it was confirmed that the photosensitivecomposition B in Examples 1B to 18B was excellent in storage stabilityand the like and also excellent in pencil hardness, adhesiveness, andthe like of a cured film.

Example 1C

<Preparation of Photosensitive Composition C (Based on PolyfunctionalMonomer, Free from Sensitizer, and Free from Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition C was prepared.

The compositions of the photosensitive composition C are based on apolyfunctional monomer (that is, a polyfunctional radicallypolymerizable monomer, the same applies to hereinafter) and do not havea sensitizer and a colorant.

—Compositions of Photosensitive Composition C (Based on PolyfunctionalMonomer, Free from Sensitizer, and Free from Colorant)—

DPGDA (polyfunctional monomer) described below 35.0% by mass  HDDA(polyfunctional monomer) described below 20.0% by mass  DVE3(polyfunctional monomer) described below 12.9% by mass  VEEA(polyfunctional monomer) described below 15.0% by mass  DPHA(polyfunctional monomer) described below 1.0% by mass CN964 (urethaneoligomer having polymerizable group, manufactured by Sartomer 2.0% bymass Company) described below IRGACURE 819 (photopolymerizationinitiator manufactured by BASF Japan Ltd., 5.0% by mass acyl phosphineoxide compound, specifically,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) IRGACURE 184(photopolymerization initiator manufactured by BASF Japan Ltd., 3.0% bymass carbonyl compound, specifically,1-hydroxy-cyclohexyl-phenyl-ketone) FIRSTCURE ST-1 (polymerizationinhibitor manufactured by Albemarle Corporation, 0.1% by masstris(N-nitroso-N-phenylhydroxylamine)aluminum salts) BYK-UV3575(modified polydimethylsiloxane surfactant manufactured by BYK 1.0% bymass Chemie GmbH) Resin listed in Table 3 5.0% by mass

<Evaluation of Photosensitive Composition C>

Evaluation was performed in the same manner as in Example 1A except thatthe photosensitive composition C was used in place of the photosensitivecomposition A.

The results are listed in Table 3.

Examples 2C to 26C

Operations which were the same as those in Example 1C were performedexcept that the kind of resin (the kind of structural unit, thecopolymerization ratio, and Mw) in the compositions of thephotosensitive composition C was changed as listed in Table 3.

The results are listed in Table 3.

Comparative Examples 1C to 5C

Operations which were the same as those in Example 1C were performedexcept that the kind of resin in the compositions of the photosensitivecomposition C was changed as listed in Table 3.

The results are listed in Table 3.

In Comparative Examples 1C to 5C, the comparative resins a to d and thecomparative compound e are as described above.

TABLE 3 Photosensitive composition C (based on polyfunctional monomer,free from sensitizer, and free from colorant) Resin Content Copoly-based on Struc- merization total amount Evaluation results turalStructural ratio of Pencil Adhesiveness unit A unit B (% by mass)composition hard- Blocking A- Storage Jetting a1 b1 b2 a1 b1 b2 Mw (% bymass) ness resistance PVC PET Acryl PC PS stability stability Example 1C(1-1) (3-1) 50 50 0 10000 5.0 H 4 0 1 1 0 1 4 4 Example 2C (1-1) (3-2)50 50 0 10000 5.0 H 4 0 1 1 0 1 4 4 Example 3C (1-2) (5-2) 50 50 0 100005.0 H 5 0 0 0 0 0 4 4 Example 4C (1-1) (3-3) 50 50 0 10000 5.0 H 5 0 1 00 1 4 4 Example 5C (1-1) (3-4) 50 50 0 10000 5.0 H 5 0 1 0 0 1 4 4Example 6C (1-1) (3-5) 50 50 0 10000 5.0 H 5 0 1 0 0 1 4 4 Example 7C(1-1) (4-1) 50 50 0 10000 5.0 2H 5 0 1 0 0 0 4 4 Example 8C (1-1) (4-2)50 50 0 10000 5.0 2H 5 0 1 0 0 0 4 4 Example 9C (1-1) (5-2) 20 80 010000 5.0 2H 4 0 0 0 0 0 4 4 Example 10C (1-1) (5-2) 30 70 0 10000 5.02H 5 0 0 0 0 0 4 4 Example 11C (1-1) (5-2) 50 50 0 10000 5.0 2H 5 0 0 00 0 4 4 Example 12C (1-1) (5-2) 70 30 0 10000 5.0 2H 5 0 0 0 0 0 4 4Example 13C (1-1) (5-1) 50 50 0 10000 5.0 2H 5 0 1 0 0 0 4 4 Example 14C(1-1) (5-1) 70 30 0 10000 5.0 2H 5 0 1 0 0 0 4 4 Example 15C (1-1) (4-3)30 70 0 10000 5.0 2H 5 0 0 0 0 0 4 4 Example 16C (1-1) (4-3) 50 50 010000 5.0 2H 5 0 0 0 0 0 4 4 Example 17C (1-1) (4-3) 70 30 0 10000 5.02H 5 0 0 0 0 0 4 4 Example 18C (1-1) (5-2) (4-3) 50 30 20 10000 5.0 2H 50 0 0 0 0 4 4 Example 19C (1-1) (5-2) (4-3) 40 40 20 10000 5.0 2H 5 0 00 0 0 4 4 Example 20C (1-1) (5-2) (4-3) 60 20 20 10000 5.0 2H 5 0 0 0 00 4 4 Example 21C (1-1) (5-2) 50 50 0 5000 5.0 2H 5 0 0 0 0 0 4 4Example 22C (1-1) (5-2) 50 50 0 25000 5.0 2H 5 0 0 0 0 0 4 4 Example 23C(1-1) (5-2) 50 50 0 40000 5.0 2H 5 0 0 0 0 0 4 4 Example 24C (1-1) (4-3)50 50 0 3000 5.0 2H 5 0 0 0 0 0 4 4 Example 25C (1-1) (4-3) 50 50 017000 5.0 2H 5 0 0 0 0 0 4 4 Example 26C (1-1) (4-3) 50 50 0 50000 5.02H 5 0 0 0 0 0 4 4 Comparative Comparative resin a 33000 5.0 3B 2 3 4 55 5 1 1 Example 1C Comparative Comparative resin b 15000 5.0 2B 3 3 4 44 4 1 1 Example 2C Comparative Comparative resin c 12000 5.0 3B 2 3 4 44 4 1 2 Example 3C Comparative Comparative resin d 60000 5.0 3B 1 3 5 55 5 1 1 Example 4C Comparative Comparative compound e 5.0 2B 2 4 5 5 5 53 3 Example 5C

As listed in Table 3, it was confirmed that the photosensitivecomposition C in Examples 1C to 26C was in the range in which thestorage stability and the like were acceptable for practical use and wasalso excellent in pencil hardness of a cured film, adhesiveness of acured film to each substrate, and the like.

Example 1D

<Preparation of Photosensitive Composition D (Based on MonofunctionalMonomer, Free from Sensitizer, and Having Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition D was prepared.

The compositions of the photosensitive composition D are based on amonofunctional monomer, do not have a sensitizer, and have a colorant.

The photosensitive composition D in Example 1D is a composition having acyan (C) color, which contains a cyan (C) pigment as a colorant. Thecolor of the composition is listed in Table 4.

Evaluation was performed in the same manner as in Example 1A except thatthe photosensitive composition D was used in place of the photosensitivecomposition A. The results are listed in Table 4.

—Compositions of Photosensitive Composition D (Based on MonofunctionalMonomer, Free from Sensitizer, and Having Colorant)—

TMCHA (monofunctional monomer) 13.0% by mass  DCPA (monofunctionalmonomer) 13.0% by mass  IBOA (monofunctional monomer) 18.9% by mass CTFA (monofunctional monomer) 21.0% by mass  PEA (monofunctionalmonomer) 6.0% by mass CN964 (urethane oligomer having polymerizablegroup, manufactured by Sartomer 2.0% by mass Company) IRGACURE 819(photopolymerization initiator manufactured by BASF Japan Ltd., 5.0% bymass acyl phosphine oxide compound, specifically,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) IRGACURE 184(photopolymerization initiator manufactured by BASF Japan Ltd., 3.0% bymass carbonyl compound, specifically,1-hydroxy-cyclohexyl-phenyl-ketone) FIRSTCURE ST-1 (polymerizationinhibitor manufactured by Albemarle Corporation, 0.1% by masstris(N-nitroso-N-phenylhydroxylamine)aluminum salts) BYK-UV3575(modified polydimethylsiloxane surfactant manufactured by BYK 1.0% bymass Chemie GmbH) C (cyan) pigment dispersion liquid 12.0% by mass Resin listed in Table 4 5.0% by mass

<Preparation of Pigment Dispersion Liquid>

In Example 1D and respective examples and comparative examples describedbelow, in examples in which the colors of the compositions weredescribed as yellow (Y), magenta (M), cyan (C), and black (K), a yellow(Y) pigment dispersion liquid, a magenta (M) pigment dispersion liquid,a cyan (C) pigment dispersion liquid, and a black (K) pigment dispersionliquid described below were respectively used as a pigment dispersionliquid. Hereinafter, a method of preparing these pigment dispersionliquids is described.

The following pigment (colorant), dispersant, and polymerizable monomerwere mixed with each other and stirred for 10 minutes at 2,500 rev/minusing a mixer (L4R, manufactured by Silverson Machine Ltd.), therebyobtaining a mixture. Thereafter, the obtained mixture was put into abead mill disperser DISPERMAT LS (manufactured by VMA Getzmann GmbH) anddispersed at 2,500 rev/min for 6 hours using a YTZ ball (manufactured byNIKKATO CORPORATION) having a diameter of 0.65 mm, thereby preparingrespective pigment dispersion liquids (Y, M, C, and K).

-Yellow (Y) pigment dispersion liquid- Pigment: C.I. Pigment Yellow 12(yellow pigment, manufactured by CLARIANT) 10 parts Dispersant:Solsperse 32000 (polymer dispersant, manufactured by Lubrizol  5 partsCorporation) Polymerizable monomer: 2-phenoxyethyl acrylate 85 parts-Magenta (M) pigment dispersion liquid- Pigment: C.I. Pigment Red 57:1(magenta pigment, manufactured by CLARIANT) 15 parts Dispersant:Solsperse 32000 (polymer dispersant, manufactured by Lubrizol  5 partsCorporation) Polymerizable monomer: 2-phenoxyethyl acrylate 80 parts-Cyan (C) pigment dispersion liquid- Pigment: C.I. Pigment Blue 15:3(cyan pigment, manufactured by CLARIANT) 20 parts Dispersant: Solsperse32000 (polymer dispersant, manufactured by Lubrizol  5 partsCorporation) Polymerizable monomer: 2-phenoxyethyl acrylate 75 parts-Black (K) pigment dispersion liquid- Pigment: C.I. Pigment Black 7(black pigment, manufactured by CLARIANT) 20 parts Dispersant: Solsperse32000 (polymer dispersant, manufactured by Lubrizol  5 partsCorporation) Polymerizable monomer: 2-phenoxyethyl acrylate 75 parts

Examples 2D to 51D

Operations which were the same as those in Example 1D were performedexcept that at least one of the kind of resin (the kind of structuralunit, the copolymerization ratio, and Mw), the content of the resinbased on the total amount of the composition (hereinafter, also simplyreferred to as the “content of a resin”), and the color of thecomposition (that is, the kind of pigment dispersion liquid) in thecompositions of the photosensitive composition D was changed as listedin Table 4.

The results are listed in Table 4.

In an example in which the content of the resin was changed, the totalamount of the resin and monomers was set to be the same as in Example 1Aby setting the compositional ratio of monomers to be constant andchanging the total amount of the monomers.

Comparative Examples 1D to 5D

Operations which were the same as those in Example 1D were performedexcept that the kind of resin in the compositions of the photosensitivecomposition D was changed as listed in Table 4.

The results are listed in Table 4.

In Comparative Examples 1D to 5D, the comparative resins a to d and acomparative compound e are as described above.

TABLE 4 Photosensitive composition D (based on monofunctional monomer,free from sensitizer, and having colorant) Resin Content based on totalStructural Structural Copolymerization amount of unit A unit B ratio (%by mass) composition a1 b1 b2 a1 b1 b2 Mw (% by mass) Color Example 1D(1-1) (3-1) 50 50 0 10000 5.0 C Example 2D (1-1) (3-2) 50 50 0 10000 5.0C Example 3D (1-2) (5-2) 50 50 0 10000 5.0 C Example 4D (1-3) (5-2) 5050 0 10000 5.0 C Example 5D (1-4) (5-2) 50 50 0 10000 5.0 C Example 6D(1-5) (5-2) 50 50 0 10000 5.0 C Example 7D (1-6) (5-2) 50 50 0 10000 5.0C Example 8D (1-7) (5-2) 50 50 0 10000 5.0 C Example 9D (1-8) (5-2) 5050 0 10000 5.0 C Example 10D (2-1) (5-2) 50 50 0 10000 5.0 C Example 11D(1-1) (4-4) 50 50 0 10000 5.0 C Example 12D (1-1) (5-3) 50 50 0 100005.0 C Example 13D (1-1) (3-3) 50 50 0 10000 5.0 C Example 14D (1-1)(3-4) 50 50 0 10000 5.0 C Example 15D (1-1) (3-5) 50 50 0 10000 5.0 CExample 16D (1-1) (4-1) 50 50 0 10000 5.0 C Example 17D (1-1) (4-1) 4060 0 10000 5.0 C Example 18D (1-1) (4-1) 60 40 0 10000 5.0 C Example 19D(1-1) (4-2) 50 50 0 10000 5.0 M Example 20D (1-1) (4-2) 70 30 0 100005.0 M Example 21D (1-1) (4-2) 30 70 0 10000 5.0 M Example 22D (1-1)(5-2) 20 80 0 10000 5.0 Y Example 23D (1-1) (5-2) 10 90 0 10000 5.0 YExample 24D (1-1) (5-2) 30 70 0 10000 5.0 Y Example 25D (1-1) (5-2) 5050 0 10000 5.0 Y Example 26D (1-1) (5-2) 70 30 0 10000 5.0 Y Example 27D(1-1) (5-2) 80 20 0 10000 5.0 Y Example 28D (1-1) (5-2) 90 10 0 100005.0 Y Example 29D (1-1) (5-1) 20 80 0 10000 5.0 K Example 30D (1-1)(5-1) 30 70 0 10000 5.0 K Example 31D (1-1) (5-1) 50 50 0 10000 5.0 KExample 32D (1-1) (5-1) 70 30 0 10000 5.0 K Example 33D (1-1) (5-1) 8020 0 10000 5.0 K Example 34D (1-1) (4-3) 20 80 0 10000 5.0 C Example 35D(1-1) (4-3) 30 70 0 10000 5.0 C Example 36D (1-1) (4-3) 50 50 0 100005.0 C Example 37D (1-1) (4-3) 70 30 0 10000 5.0 C Example 38D (1-1)(4-3) 80 20 0 10000 5.0 C Example 39D (1-1) (5-2) (4-3) 50 30 20 100005.0 K Example 40D (1-1) (5-2) (4-3) 40 40 20 10000 5.0 K Example 41D(1-1) (5-2) (4-3) 60 20 20 10000 5.0 K Example 42D (1-1) (5-2) 50 50 05000 5.0 C Example 43D (1-1) (5-2) 50 50 0 25000 5.0 C Example 44D (1-1)(5-2) 50 50 0 40000 5.0 C Example 45D (1-1) (4-3) 50 50 0 3000 5.0 CExample 46D (1-1) (4-3) 50 50 0 17000 5.0 C Example 47D (1-1) (4-3) 5050 0 50000 5.0 C Example 48D (1-1) (5-2) 50 50 0 10000 0.5 Y Example 49D(1-1) (5-2) 50 50 0 10000 2.0 Y Example 50D (1-1) (5-2) 50 50 0 100007.0 Y Example 51D (1-1) (5-2) 50 50 0 10000 10.0 Y ComparativeComparative resin a 33000 5.0 C Example 1D Comparative Comparative resinb 15000 5.0 C Example 2D Comparative Comparative resin c 12000 5.0 CExample 3D Comparative Comparative resin d 60000 5.0 C Example 4DComparative Comparative compound e 5.0 C Example 5D Photosensitivecomposition D (based on monofunctional monomer, free from sensitizer,and having colorant) Evaluation results Adhesiveness Pencil Blocking A-Storage Jetting hardness resistance PVC PET Acryl PC PS stabilitystability Example 1D F 4 0 1 1 0 1 5 5 Example 2D F 4 0 1 1 0 1 5 5Example 3D F 5 0 0 0 0 0 5 5 Example 4D F 4 0 0 0 0 0 5 5 Example 5D F 50 0 0 0 0 5 5 Example 6D F 4 0 0 0 0 0 5 5 Example 7D F 4 0 0 0 0 0 5 5Example 8D F 4 0 0 0 0 0 5 5 Example 9D F 5 0 0 0 0 0 5 5 Example 10D F4 0 0 0 0 0 5 5 Example 11D F 5 0 1 0 0 1 5 5 Example 12D F 5 0 1 0 0 15 5 Example 13D F 5 0 1 0 0 1 5 5 Example 14D F 5 0 1 0 0 1 5 5 Example15D F 5 0 1 0 0 1 5 5 Example 16D H 5 0 1 0 0 0 5 5 Example 17D H 5 0 10 0 0 5 5 Example 18D H 5 0 1 0 0 0 5 5 Example 19D H 5 0 1 0 0 0 5 5Example 20D H 5 0 1 0 0 0 5 5 Example 21D H 5 0 1 0 0 0 5 5 Example 22DH 4 0 0 0 0 0 5 5 Example 23D H 4 0 1 1 0 0 5 5 Example 24D H 5 0 0 0 00 5 5 Example 25D H 5 0 0 0 0 0 5 5 Example 26D H 5 0 0 0 0 0 5 5Example 27D H 5 0 1 1 0 0 5 5 Example 28D H 5 0 1 1 1 0 5 5 Example 29DH 4 0 1 0 0 1 5 5 Example 30D H 5 0 1 0 0 0 5 5 Example 31D H 5 0 1 0 00 5 5 Example 32D H 5 0 1 0 0 0 5 5 Example 33D H 5 0 1 1 0 0 5 5Example 34D H 4 0 0 0 0 1 5 5 Example 35D H 5 0 0 0 0 0 5 5 Example 36DH 5 0 0 0 0 0 5 5 Example 37D H 5 0 0 0 0 0 5 5 Example 38D H 5 0 1 1 00 5 5 Example 39D H 5 0 0 0 0 0 5 5 Example 40D H 5 0 0 0 0 0 5 5Example 41D H 5 0 0 0 0 0 5 5 Example 42D H 5 0 0 0 0 0 5 5 Example 43DH 5 0 0 0 0 0 5 5 Example 44D H 5 0 0 0 0 0 5 5 Example 45D H 5 0 0 0 00 5 5 Example 46D H 5 0 0 0 0 0 5 5 Example 47D H 5 0 0 0 0 0 5 5Example 48D F 5 0 0 0 0 0 5 5 Example 49D H 5 0 0 0 0 0 5 5 Example 50DH 5 0 0 0 0 0 5 5 Example 51D H 5 0 0 0 0 0 5 4 Comparative 3B 2 3 4 5 55 1 2 Example 1D Comparative 2B 3 3 4 4 4 4 1 1 Example 2D Comparative3B 2 3 4 4 4 4 1 3 Example 3D Comparative 3B 1 3 5 5 5 5 2 1 Example 4DComparative 2B 2 4 5 5 5 5 4 4 Example 5D

As listed in Table 4, it was confirmed that the photosensitivecomposition D in Examples 1D to 51D was excellent in storage stabilityand the like and also excellent in pencil hardness, adhesiveness, andthe like of a cured film.

Example 1E

<Preparation of Photosensitive Composition E (Based on MonofunctionalMonomer, Having Sensitizer, and Having Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition E was prepared.

The compositions of the photosensitive composition E are based on amonofunctional monomer, have a sensitizer, and have a colorant.

The photosensitive composition E in Example 1E is a composition having acyan (C) color, which contains a cyan (C) pigment as a colorant. Thecolor of the composition is listed in Table 5.

—Compositions of Photosensitive Composition E (Based on MonofunctionalMonomer, Having Sensitizer, and Having Colorant)—

IBOA (monofunctional monomer) 25.0% by mass  CTFA (monofunctionalmonomer) 25.0% by mass  PEA (monofunctional monomer) 17.9% by mass CN964 (urethane oligomer having polymerizable group, manufactured bySartomer 2.0% by mass Company) IRGACURE 819 (photopolymerizationinitiator manufactured by BASF Japan Ltd., 5.0% by mass acyl phosphineoxide compound, specifically,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) IRGACURE 184(photopolymerization initiator manufactured by BASF Japan Ltd., 3.0% bymass carbonyl compound, specifically,1-hydroxy-cyclohexyl-phenyl-ketone) ITX (sensitizer,2-isopropylthioxanthone) 1.0% by mass BP (sensitizer, benzophenone) 2.0%by mass EDB (sensitizer, ethyl 4-(dimethylamino)benzoate) 1.0% by massFIRSTCURE ST-1 (polymerization inhibitor manufactured by Albemarle 0.1%by mass Corporation) BYK-UV3575 (modified polydimethylsiloxanesurfactant manufactured by BYK 1.0% by mass Chemie GmbH) Cyan (C)pigment dispersion liquid 12.0% by mass  Resin listed in Table 5 5.0% bymass

<Evaluation of Photosensitive Composition E>

Evaluation was performed in the same manner as in Example 1A except thatthe photosensitive composition E was used in place of the photosensitivecomposition A and the exposure device and the exposure conditions werechanged as shown below.

The results are listed in Table 5.

In the evaluation of the photosensitive composition E, a 385 nm UV-LEDirradiator (manufactured by CCS Inc.) for a test was used as an exposuredevice and an exposure energy of 300 mJ/cm² was set as the exposurecondition.

Examples 2E to 22E

Operations which were the same as those in Example 1E were performedexcept that the kind of resin (the kind of structural unit, thecopolymerization ratio, and Mw) and the color of the composition (thatis, the kind of pigment dispersion liquid) in the compositions of thephotosensitive composition E were changed as listed in Table 5.

The results are listed in Table 5.

In examples in which the colors of the compositions were described asyellow (Y), magenta (M), and black (K), a yellow (Y) pigment dispersionliquid, a magenta (M) pigment dispersion liquid, and a black (K) pigmentdispersion liquid described above were respectively used as a pigmentdispersion liquid.

Comparative Examples 1E to 5E

Operations which were the same as those in Example 1E were performedexcept that the kind of resin in the compositions of the photosensitivecomposition E was changed as listed in Table 5.

The results are listed in Table 5.

In Comparative Examples 1E to 5E, the comparative resins a to d and thecomparative compound e are as described above.

TABLE 5 Photosensitive composition E (based on monofunctional monomer,having sensitizer, and having colorant) Resin Content based on totalStructural Structural Copolymerization amount of unit A unit B ratio (%by mass) composition a1 b1 b2 a1 b1 b2 Mw (% by mass) Color Example 1E(1-1) (3-1) 50 50 0 10000 5.0 C Example 2E (1-1) (3-3) 50 50 0 10000 5.0C Example 3E (1-1) (3-4) 50 50 0 10000 5.0 C Example 4E (1-1) (3-5) 5050 0 10000 5.0 C Example 5E (1-1) (4-1) 50 50 0 10000 5.0 M Example 6E(1-1) (4-2) 50 50 0 10000 5.0 Y Example 7E (1-1) (5-2) 30 70 0 10000 5.0Y Example 8E (1-1) (5-2) 50 50 0 10000 5.0 Y Example 9E (1-1) (5-2) 7030 0 10000 5.0 Y Example (1-1) (4-1) 50 50 0 10000 5.0 Y 10E Example(1-1) (4-1) 70 30 0 10000 5.0 K 11E Example (1-1) (4-3) 50 50 0 100005.0 C 12E Example (1-1) (4-3) 70 30 0 10000 5.0 C 13E Example (1-1)(5-2) (4-3) 50 30 20 10000 5.0 K 14E Example (1-1) (5-2) (4-3) 50 30 2010000 5.0 K 15E Example (1-1) (5-2) (4-3) 50 30 20 10000 5.0 K 16EExample (1-1) (5-2) 50 50 0 5000 5.0 C 17E Example (1-1) (5-2) 50 50 025000 5.0 C 18E Example (1-1) (5-2) 50 50 0 40000 5.0 C 19E Example(1-1) (4-3) 50 50 0 3000 5.0 C 20E Example (1-1) (4-3) 50 50 0 17000 5.0C 21E Example (1-1) (4-3) 50 50 0 50000 5.0 C 22E ComparativeComparative resin a 33000 5.0 C Example 1E Comparative Comparative resinb 15000 5.0 C Example 2E Comparative Comparative resin c 12000 5.0 CExample 3E Comparative Comparative resin d 60000 5.0 C Example 4EComparative Comparative compound e 5.0 C Example 5E Photosensitivecomposition E (based on monofunctional monomer, having sensitizer, andhaving colorant) Evaluation results Adhesiveness Pencil Blocking A-Storage Jetting hardness resistance PVC PET Acryl PC PS stabilitystability Example 1E F 4 0 1 1 0 1 5 5 Example 2E F 4 0 1 1 0 1 5 5Example 3E F 5 0 1 0 0 1 5 5 Example 4E H 5 0 1 0 0 0 5 5 Example 5E H 50 1 0 0 0 5 5 Example 6E H 4 0 0 0 0 0 5 5 Example 7E H 5 0 0 0 0 0 5 5Example 8E H 5 0 0 0 0 0 5 5 Example 9E H 5 0 0 0 0 0 5 5 Example H 5 01 1 0 0 5 5 10E Example H 5 0 1 0 0 0 5 5 11E Example H 5 0 0 0 0 0 5 512E Example H 5 0 0 0 0 0 5 5 13E Example H 5 0 0 0 0 0 5 5 14E ExampleH 5 0 0 0 0 0 5 5 15E Example H 5 0 0 0 0 0 5 5 16E Example H 5 0 0 0 00 5 5 17E Example H 5 0 0 0 0 0 5 5 18E Example H 5 0 0 0 0 0 5 4 19EExample H 5 0 0 0 0 0 5 5 20E Example H 5 0 0 0 0 0 5 5 21E Example H 50 0 0 0 0 5 4 22E Comparative 3B 2 3 4 5 5 5 1 2 Example 1E Comparative2B 3 3 4 4 4 4 1 1 Example 2E Comparative 3B 2 3 4 4 4 4 1 3 Example 3EComparative 3B 1 3 5 5 5 5 2 1 Example 4E Comparative 2B 2 4 5 5 5 5 4 4Example 5E

As listed in Table 5, it was confirmed that the photosensitivecomposition E in Examples 1E to 22E was excellent in storage stabilityand the like and also excellent in pencil hardness, adhesiveness, andthe like of a cured film.

Particularly, from the results of Examples 18E to 22E, from theviewpoint of the jetting stability, it is understood that the Mw of theresin is preferably in a range of 1000 to 30000.

Example 1F

<Preparation of Photosensitive Composition F (Based on PolyfunctionalMonomer, Free from Sensitizer, and Having Colorant)>

Respective components of the following compositions were mixed with eachother and a photosensitive composition F was prepared.

The compositions of the photosensitive composition F are based on apolyfunctional monomer, do not have a sensitizer, and have a colorant.

—Compositions of Photosensitive Composition F (Based on PolyfunctionalMonomer, Free from Sensitizer, and Free from Colorant)—

DPGDA (polyfunctional monomer) 35.0% by mass  HDDA (polyfunctionalmonomer) 20.0% by mass  DVE3 (polyfunctional monomer) 12.9% by mass VEEA (polyfunctional monomer) 15.0% by mass  DPHA (polyfunctionalmonomer) 1.0% by mass CN964 (urethane oligomer having polymerizable 2.0%by mass group, manufactured by Sartomer Company) IRGACURE 819(photopolymerization initiator 5.0% by mass manufactured by BASF JapanLtd., acyl phosphine oxide compound, specifically, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) IRGACURE 184(photopolymerization initiator 3.0% by mass manufactured by BASF JapanLtd., carbonyl compound, specifically, 1-hydroxy-cyclohexyl-phenyl-ketone) FIRSTCURE ST-1 (polymerization inhibitor 0.1% by massmanufactured by Albemarle Corporation,tris(N-nitroso-N-phenylhydroxylamine)aluminum salts) BYK-UV3575(modified polydimethylsiloxane 1.0% by mass surfactant manufactured byBYK Chemie GmbH) Cyan (C) pigment dispersion liquid 12.0% by mass  Resinlisted in Table 6 5.0% by mass

<Evaluation of Photosensitive Composition F>

Evaluation was performed in the same manner as in Example 1A except thatthe photosensitive composition F was used in place of the photosensitivecomposition A.

The results are listed in Table 6.

Examples 2F to 22F

Operations which were the same as those in Example 1F were performedexcept that the kind of resin (the kind of structural unit, thecopolymerization ratio, and Mw) and the color of the composition (thatis, the kind of pigment dispersion liquid) in the compositions of thephotosensitive composition F were changed as listed in Table 6.

The results are listed in Table 6.

In examples in which the colors of the compositions were described asyellow (Y), magenta (M), and black (K), a yellow (Y) pigment dispersionliquid, a magenta (M) pigment dispersion liquid, and a black (K) pigmentdispersion liquid described above were respectively used as a pigmentdispersion liquid.

Comparative Examples 1F to 5F

Operations which were the same as those in Example 1F were performedexcept that the kind of resin in the compositions of the photosensitivecomposition F was changed as listed in Table 6.

The results are listed in Table 6.

In Comparative Examples 1F to 5F, the comparative resins a to d and thecomparative compound e are as described above.

TABLE 6 Photosensitive composition F (based on polyfunctional monomer,free from sensitizer, and having colorant) Resin Content based on totalamount of Structural Structural Copolymerization composition unit A unitB ratio (% by mass) (% by a1 b1 b2 a1 b1 b2 Mw mass) Color Example 1F(1-1) (3-1) 50 50 0 10000 5.0 C Example 2F (1-1) (3-3) 50 50 0 10000 5.0C Example 3F (1-1) (4-1) 60 40 0 10000 5.0 C Example 4F (1-1) (4-2) 7030 0 10000 5.0 M Example 5F (1-1) (5-2) 20 80 0 10000 5.0 Y Example 6F(1-1) (5-2) 30 70 0 10000 5.0 Y Example 7F (1-1) (5-2) 50 50 0 10000 5.0Y Example 8F (1-1) (5-2) 70 30 0 10000 5.0 Y Example 9F (1-1) (5-2) 8020 0 10000 5.0 Y Example (1-1) (5-1) 20 80 0 10000 5.0 K 10F Example(1-1) (5-1) 50 50 0 10000 5.0 K 11F Example (1-1) (5-1) 80 20 0 100005.0 K 12F Example (1-1) (4-3) 30 70 0 10000 5.0 C 13F Example (1-1)(4-3) 70 30 20 10000 5.0 C 14F Example (1-1) (5-2) (4-3) 50 30 20 100005.0 K 15F Example (1-1) (5-2) (4-3) 40 40 20 10000 5.0 K 16F Example(1-1) (5-2) 50 50 0 5000 5.0 C 17F Example (1-1) (5-2) 50 50 0 25000 5.0C 18F Example (1-1) (5-2) 50 50 0 40000 5.0 C 19F Example (1-1) (4-3) 5050 0 3000 5.0 C 20F Example (1-1) (4-3) 50 50 0 17000 5.0 C 21F Example(1-1) (4-3) 50 50 0 50000 5.0 C 22F Comparative Comparative resin a33000 5.0 C Example 1F Comparative Comparative resin b 15000 5.0 CExample 2F Comparative Comparative resin c 12000 5.0 C Example 3FComparative Comparative resin d 60000 5.0 C Example 4F ComparativeComparative compound e 5.0 C Example 5F Photosensitive composition F(based on polyfunctional monomer, free from sensitizer, and havingcolorant) Evaluation results Adhesiveness Pencil Blocking A- StorageJetting hardness resistance PVC PET Acryl PC PS stability stabilityExample 1F H 4 0 1 1 0 1 4 4 Example 2F H 5 0 1 0 0 1 4 4 Example 3F 2H5 0 1 0 0 0 4 4 Example 4F 2H 5 0 1 0 0 0 4 4 Example 5F 2H 4 0 0 0 0 04 4 Example 6F 2H 5 0 0 0 0 0 4 4 Example 7F 2H 5 0 0 0 0 0 4 4 Example8F 2H 5 0 0 0 0 0 4 4 Example 9F 2H 5 0 1 1 0 0 4 4 Example 2H 4 0 1 0 01 4 4 10F Example 2H 5 0 1 0 0 0 4 4 11F Example 2H 5 0 1 1 0 0 4 4 12FExample 2H 5 0 0 0 0 0 4 4 13F Example 2H 5 0 0 0 0 0 4 4 14F Example 2H5 0 0 0 0 0 4 4 15F Example 2H 5 0 0 0 0 0 4 4 16F Example 2H 5 0 0 0 00 4 4 17F Example 2H 5 0 0 0 0 0 4 4 18F Example 2H 5 0 0 0 0 0 4 4 19FExample 2H 5 0 0 0 0 0 4 4 20F Example 2H 5 0 0 0 0 0 4 4 21F Example 2H5 0 0 0 0 0 4 4 22F Comparative 3B 2 3 4 5 5 5 1 1 Example 1FComparative 2B 3 3 4 4 4 4 1 1 Example 2F Comparative 3B 2 3 4 4 4 4 1 2Example 3F Comparative 3B 1 3 5 5 5 5 1 1 Example 4F Comparative 2B 2 45 5 5 5 3 3 Example 5F

As listed in Table 6, it was confirmed that the photosensitivecomposition F in Examples 1F to 22F was in the range in which thestorage stability and the like were acceptable for practical use and wasalso excellent in pencil hardness of a cured film, adhesiveness of acured film, and the like.

Example 1G

<Preparation of Photosensitive Composition G (Based on PolyfunctionalMonomer, Free from Sensitizer, and Having Colorant)>

Respective components of the following compositions were mixed with eachother by changing the cyan (C) pigment dispersion liquid to a yellow (Y)pigment dispersion liquid in the composition of the photosensitivecomposition F described above and further changing the resin to theresin listed in Table 7, thereby preparing a photosensitive compositionG.

(Re-Jetting Properties after Photosensitive Composition G being Left toStand)

After the photosensitive composition G (ink) was jetted (first jetting)for 30 minutes under the following jetting conditions using acommercially available ink jet recording device (LuxelJet (registeredtrademark) UV3600GT/XT: trade name, manufactured by FujifilmCorporation) including a piezoelectric ink jetting head, the jetting wasstopped.

After a predetermined time elapsed since the jetting was stopped, a 100%solid image having a size of 5 cm×5 cm was formed by jetting the inkagain from the head onto a polyethylene terephthalate (PET) film(manufactured by Toray Industries, Inc.) serving as a substrate andirradiating the impacted ink with UV light (irradiation dose: 1000mW/cm²).

The obtained image was visually observed, the presence of dot lossresulting from occurrence of nozzles with jetting failure was confirmed,and re-jetting properties after the composition was left to stand wereevaluated.

<Jetting Conditions>

-   -   Number of channels: 318/head    -   Drive frequency: 4.8 kHz/dot    -   Ink drops: 7 drops, 42 pl    -   Temperature of head nozzle: 45° C.

<Evaluation Standard of Re-jetting Properties after being Left to Stand>

3: In jetting after 5 minutes from the first jetting, occurrence of dotloss resulting from the occurrence of nozzles with jetting failure wasnot found and an excellent image was obtained.

2: In jetting after 3 minutes from the first jetting, occurrence of dotloss resulting from the occurrence of nozzles with jetting failure wasnot found and an excellent image was obtained. However, in jetting after4 minutes from the first jetting, occurrence of dot loss to the extentthat does not inhibit practical use was slightly found.

1: In jetting after 2 minutes from the first jetting, occurrence of dotloss resulting from the occurrence of nozzles with jetting failure wasnot found and an excellent image was obtained. However, in jetting after3 minutes from the first jetting, occurrence of dot loss to the extentthat does not inhibit practical use was slightly found.

Other evaluations of the photosensitive composition G were performed inthe same manner as in Example 1A.

TABLE 7 Photosensitive composition G (based on polyfunctional monomer,free from sensitizer, and having colorant) Resin Content based on totalamount of Structural Structural Copolymerization composition unit A unitB ratio (% by mass) (% by a1 b1 b2 a1 b1 b2 Mw mass) Color Example 1G(1-1) (5-2) — 70 30 — 10000 50 Y Example 2G (1-1) (5-2) (3-3) 60 10 3010000 50 Y Example 3G (1-1) (5-2) (3-4) 60 10 30 10000 50 Y Example 4G(1-1) (5-2) (3-5) 60 10 30 10000 50 Y Example 5G (1-1) (5-1) (3-3) 60 1030 10000 50 Y Example 6G (1-1) (4-3) (3-3) 60 10 30 10000 50 YPhotosensitive composition G (based on polyfunctional monomer, free fromsensitizer, and having colorant) Evaluation results Re-jettingproperties Adhesiveness after Pencil Blocking A- Storage Jetting beingleft hardness resistance PVC PET Acryl PC PS stability stability tostand Example 2H 5 0 0 0 0 0 4 4 1 1G Example 2H 5 0 0 0 0 0 4 5 3 2GExample 2H 5 0 0 0 0 0 4 5 3 3G Example 2H 5 0 0 0 0 0 4 5 3 4G Example2H 5 0 0 0 0 0 4 5 2 5G Example 2H 5 0 0 0 0 0 4 5 2 6G

The disclosure of JP No. 2015-167974 filed on Aug. 27, 2015 isincorporated herein by reference.

In a case where all documents, patent applications, and technicalstandards described in the present specification are specified to beincorporated specifically and individually as cited documents, thedocuments, patent applications, and technical standards are incorporatedherein in the same limited scope as the cited documents. The scope ofthe present invention is intended to be determined based on thefollowing claims and the equivalents thereof.

What is claimed is:
 1. A photosensitive composition containing: a resinwhich includes a structural unit A represented by Formula (1) or (2) anda structural unit B represented by Formula (5); and a radicallypolymerizable monomer,

wherein, in Formula (1), R¹¹ represents a hydrogen atom or a hydrocarbongroup, R¹², R¹³, and R¹⁴ each independently represent a hydrocarbongroup, which may be substituted with a halogen atom and contain anoxygen atom, a hydrogen atom, or a hydroxyl group, L¹ represents asingle bond or a divalent linking group, X¹ represents a —O— group or a—NR¹⁵— group, and R¹⁵ represents a hydrogen atom or a hydrocarbon group,in Formula (2), R²¹ represents a hydrogen atom or a hydrocarbon group,R²² represents a hydrocarbon group, which may be substituted with ahalogen atom and contain an oxygen atom, a hydrogen atom, or a hydroxylgroup, R²³ and R²⁴ each independently represent a hydrocarbon group,which may be substituted with a halogen atom and contain an oxygen atom,a hydrogen atom, or a hydroxyl group or R²³ and R²⁴ are integrated torepresent an oxygen atom, L² represents a single bond or a divalentlinking group, X² represents a —O— group or a —NR²⁵— group, and R²⁵represents a hydrogen atom or a hydrocarbon group, and in Formula (5),R⁵¹ represents a hydrogen atom or a hydrocarbon group, R⁵² and R⁵³ eachindependently represent a hydrogen atom or a hydrocarbon group, and R⁵²and R⁵³ may be bonded to each other and form a ring.
 2. Thephotosensitive composition according to claim 1, wherein, in Formula(1), R¹¹ represents a hydrogen atom or an alkyl group having 1 to 3carbon atoms, R¹², R¹³, and R¹⁴ each independently represent ahydrocarbon group having 1 to 12 carbon atoms, which may be substitutedwith a halogen atom and contain an oxygen atom, a hydrogen atom, or ahydroxyl group, L¹ represents a single bond, an alkylene group having 1to 3 carbon atoms, or a group represented by any one of Formulae (L11)to (L14), and R¹⁵ represents a hydrogen atom or an alkyl group having 1to 3 carbon atoms, in Formula (2), R²¹ represents a hydrogen atom or analkyl group having 1 to 3 carbon atoms, R²² represents a hydrocarbongroup having 1 to 12 carbon atoms, which may be substituted with ahalogen atom and contain an oxygen atom, a hydrogen atom, or a hydroxylgroup, R²³ and R²⁴ each independently represent a hydrocarbon grouphaving 1 to 12 carbon atoms, which may be substituted with a halogenatom and contain an oxygen atom, a hydrogen atom, or a hydroxyl group orR²³ and R²⁴ are integrated to represent an oxygen atom, L² represents analkylene group having 1 to 3 carbon atoms or a group represented by anyone of Formulae (L21) to (L24), and R²⁵ represents a hydrogen atom or analkyl group having 1 to 3 carbon atoms, and in Formula (5) R⁵¹represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,and R⁵² and R⁵³ each independently represent a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms or R⁵² and R⁵³ are bonded to each otherand represent a group represented by Formula (N51) or (N52),

wherein, in Formula (L11), L represents an alkylene group having 1 to 3carbon atoms, n represents an integer of 1 to 4, *1 represents a bindingposition with respect to X¹, and *2 represents a binding position withrespect to a carbon atom, in Formula (L12), L represents an alkylenegroup having 1 to 3 carbon atoms, *1 represents a binding position withrespect to X¹, and *2 represents a binding position with respect to acarbon atom, in Formula (L13), L¹ and L² each independently represent analkylene group having 1 to 3 carbon atoms, *1 represents a bindingposition with respect to X¹, and *2 represents a binding position withrespect to a carbon atom, in Formula (L14), *1 represents a bindingposition with respect to X¹, and *2 represents a binding position withrespect to a carbon atom, in Formula (L21), L represents an alkylenegroup having 1 to 3 carbon atoms, n represents an integer of 1 to 4, *1represents a binding position with respect to X², and *2 represents abinding position with respect to a carbon atom, in Formula (L22), Lrepresents an alkylene group having 1 to 3 carbon atoms, *1 represents abinding position with respect to X², and *2 represents a bindingposition with respect to a carbon atom, in Formula (L23), L¹ and L² eachindependently represent an alkylene group having 1 to 3 carbon atoms, *1represents a binding position with respect to X², and *2 represents abinding position with respect to a carbon atom, in Formula (L24), *1represents a binding position with respect to X², and *2 represents abinding position with respect to a carbon atom, in Formula (L31), Lrepresents an alkylene group having 1 to 3 carbon atoms, n represents aninteger of 1 to 4, *1 represents a binding position with respect to anoxygen atom, and *2 represents a binding position with respect to Cy¹,in Formula (L32), L represents an alkylene group having 1 to 3 carbonatoms, *1 represents a binding position with respect to an oxygen atom,and *2 represents a binding position with respect to Cy¹, in Formula(L33), L¹ and L² each independently represent an alkylene group having 1to 3 carbon atoms, *1 represents a binding position with respect to anoxygen atom, and *2 represents a binding position with respect to Cy¹,in Formula (L34), *1 represents a binding position with respect to anoxygen atom, and *2 represents a binding position with respect to Cy¹,in Formulae (N41) to (N44), *1 and *2 represent a binding position withrespect to a nitrogen atom, and in Formulae (N51) and (N52), *1represents a binding position with respect to a nitrogen atom, and *2represents a binding position with respect to a carbon atom.
 3. Thephotosensitive composition according to claim 1, wherein the totalcontent of the structural unit A and the structural unit B in the resinis 80% by mass or greater based on the total amount of the resin.
 4. Thephotosensitive composition according to claim 1, wherein the proportionof the structural unit A in the total content of the structural unit Aand the structural unit B in the resin is in a range of 10% by mass to90% by mass.
 5. The photosensitive composition according to claim 1,wherein the structural unit A is at least one structural unit C selectedfrom the group consisting of a structural unit represented by Formula(1-1), a structural unit represented by Formula (1-2), a structural unitrepresented by Formula (1-3), a structural unit represented by Formula(1-4), a structural unit represented by Formula (1-5), a structural unitrepresented by Formula (1-6), a structural unit represented by Formula(1-7), a structural unit represented by Formula (1-8), and a structuralunit represented by Formula (2-1)


6. The photosensitive composition according to claim 1, wherein thestructural unit B is at least one structural unit D selected from thegroup consisting of a structural unit represented by Formula (5-1), astructural unit represented by Formula (5-2), and a structural unitrepresented by Formula (5-3)


7. The photosensitive composition according to claim 1, wherein theweight-average molecular weight of the resin is in a range of 1000 to50000.
 8. The photosensitive composition according to claim 1, whereinthe content of the resin is in a range of 0.5% by mass to 10.0% by massbased on the total amount of the photosensitive composition.
 9. Thephotosensitive composition according to claim 1, wherein the radicallypolymerizable monomer includes a monofunctional radically polymerizablemonomer.
 10. The photosensitive composition according to claim 1,wherein the content of the radically polymerizable monomer is 50% bymass or greater based on the total amount of the photosensitivecomposition.
 11. The photosensitive composition according to claim 1,further containing a photopolymerization initiator.
 12. An image formingmethod comprising: an application process of applying an ink compositionwhich is the photosensitive composition according to claim 1 onto arecording medium according to an ink-jet method; and an irradiationprocess of irradiating the ink composition applied onto the recordingmedium with active energy rays.
 13. A film forming method comprising: anapplication process of applying the photosensitive composition accordingto claim 1 onto a substrate; and an irradiation process of irradiatingthe photosensitive composition applied onto the substrate with activeenergy rays.
 14. A resin comprising: at least one structural unit Cselected from the group consisting of a structural unit represented byFormula (1-1), a structural unit represented by Formula (1-2), astructural unit represented by Formula (1-3), a structural unitrepresented by Formula (1-4), a structural unit represented by Formula(1-5), a structural unit represented by Formula (1-6), a structural unitrepresented by Formula (1-7), a structural unit represented by Formula(1-8), and a structural unit represented by Formula (2-1); and at leastone structural unit D selected from the group consisting of a structuralunit represented by Formula (5-1), a structural unit represented byFormula (5-2), and a structural unit represented by Formula (5-3)


15. An image containing: the resin according to claim
 14. 16. A filmcontaining: the resin according to claim 14.